JPH0769809A - Stickproofing agent for marine organism - Google Patents

Abstract

PURPOSE:To provide the subject stickproofing agent containing, as active ingredient, specific vanillylamine derivative (s), nontoxic to human and livestock and fishes, etc., causing no environmental pollution, also free from heavy metals and, effective at low concentrations. CONSTITUTION:This stickproofing agent for marine organisms has greatly excellent preventing activity against marine organism sticking and, contains, as active ingredient, at least one kind of vanillylamine derivatives of formula I (R is a 4-11C saturated or unsaturated hydrocarbon) (e.g. vanillyl norylamide of formula II, vanillylmethyl noneylamide of formula III). The aim of this agent can be accomplished by either of the following methods: (1) the compound of the formula I is added in small amount to a seawater cooling system during the sticking and growing of marine organisms such as Mytilus edulis; (2) fishnets are immersed in a solution containing a vanillylamine derivative to fix the compound on the fishnets, and these fishnets are used as culturing nets in marine organism sticking period; and (3) this compound is admixed with a coating film-forming material followed by coating the mixture on objects.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a marine organism adhesion preventive agent, and in particular, it is applied to an underwater structure such as a fishing net, a ship bottom, a seawater intake channel wall, or added to seawater to form a barnacle or mussel. The present invention provides a compound effective for preventing stains due to the adhesion of marine organisms such as

[0002]

2. Description of the Related Art In factories such as thermal power plants and steel plants that use seawater as cooling water, marine organisms such as mussels, barnacles, hydrops, bryozoans, etc. adhere to the cooling water system and their function deteriorates. I am letting you. An example will be described below. Blue mussels have a property of adhering to each other in multiple layers, and their growth rate is also fast, so the blue mussels attached to the bottom layer die because they cannot sufficiently ingest nutrient salts and dissolved oxygen from seawater. Due to the death of the bottom mussel, the ascidian attached to the wall becomes weak and falls off due to water pressure or water. The mussels that have fallen off cause the cooling tubes to become blocked, which impedes the passage of seawater and reduces its function.

In the aquaculture industry such as yellowtail, which has become popular in recent years, since aquaculture nets, ropes, or fixed nets are installed in the sea for a long period of time, marine organisms such as mussels, bryozoans, and ascidians adhere to the fish. I am suffering from various obstacles. An example will be described below. When a large amount of blue mussels, squirts, bryozoans, etc. adhere to the aquaculture net, the passage of seawater is obstructed, causing a shortage of dissolved oxygen in the aquaculture fish, or causing sinking or cutting of the fish net, causing the aquaculture fish to die. Damage will occur.

Further, in an underwater structure such as a ship,
Due to the adhesion of marine organisms such as barnacles and mussels,
In ships, the speed decreases due to increased resistance, and in the intake channel of seawater, the flow rate decreases. Therefore, docking or operation must be stopped at regular intervals to remove these deposits.

In order to prevent the above-mentioned various obstacles, organic tin compounds, heavy metals, organic sulfur compounds, quaternary ammonium salts and the like have hitherto been used.

[0006]

However, since the organotin compounds and heavy metals are highly toxic to humans and fishes, their use is being regulated from the viewpoint of environmental pollution. On the other hand, the other drugs mentioned above are not sufficiently effective.

The present inventors have conducted extensive studies on a marine organism adhesion-preventing agent that is neither toxic to human livestock, fish, etc., nor environmentally contaminated, and that does not contain heavy metals. As a result, a specific vanillylamine derivative satisfies the above conditions. , It has been found that it shows an extremely excellent anti-adhesion effect of marine organisms and that it is effective at lower concentrations.

[0008]

The present invention has been proposed in view of the above, and has the general formula

[Chemical 2] The present invention proposes a marine organism adhesion-preventing agent containing one or more vanillylamine derivatives represented by the formula (1) as an active ingredient.

Specific examples of the vanillylamine derivative in the present invention include, for example,

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7] Etc., these derivatives may be chemically synthesized ones, or ones extracted from a natural product may be used. For example, vanillyl nonylamide can be extracted from the mustard, but the mustard itself may be used as it is.

The vanillylamine derivative is added to a small amount of seawater cooling water system when marine organisms (such as blue mussels) adhere and grow, or by immersing and fixing the fishnet in a solution containing the vanillylamine derivative. A method of using as a net for aquaculture during the attaching period of marine organisms,
Further, the object can be achieved by a method of mixing the vanillylamine derivative in a coating film-forming material and applying it to an object.

In the method of adding a small amount of the above vanillylamine derivative to the seawater cooling water system, the vanillylamine derivative is preliminarily mixed with a suitable solvent (water, or acetone, xylene, dimethylformamide, methylcellosolve, methyl alcohol) so that the vanillylamine derivative is uniformly dispersed in the seawater. ,Ethyl alcohol,
It is preferable to dissolve or emulsify and suspend in an organic solvent such as toluene or cellosolve acetate, and to add a surfactant as necessary, and to use it as a preparation having an appropriate concentration. Examples of the above surfactants include higher fatty acid salts, polyoxyethylene alkyl ethers, sorbitan fatty acid esters, alkyl trimethyl ammonium salts, alkyl betaines and the like.

In the method of immersing and fixing in a fish net, a vanillylamine derivative is added with a natural resin, an oily synthetic resin-based vehicle or a synthetic rubber-based vehicle and a plasticizer or a solvent, or a color pigment is added and dissolved / dispersed. . As the above-mentioned natural resin or oily synthetic resin-based or synthetic rubber-based vehicle, rosin, boil oil, asphalt, coal tar, coumarone resin, vinyl chloride resin, vinyl acetate resin, polyolefin resin such as polybutene, polystyrene, acrylic Resin, polyurethane resin, amino resin, epoxy resin, phenol resin, alkyd resin,
An unsaturated polyester resin etc. can be mentioned.

In the method of mixing a vanillylamine derivative in a coating film forming material (paint) and applying it to an object, a natural resin type, a synthetic resin type or a rubber derivative type is added to the above coating film forming material as a main element for forming a coating film. Using a vehicle and adding a small amount to the above main elements to disperse the paint, dry and cure the coating, and as a film forming sub-element for improving various physical properties, a drying agent, a curing agent, a plasticizer, an emulsifying agent or a dispersing agent. The surfactant or the like can be used, and a solvent or a diluent can be used as a film forming auxiliary element for facilitating application of the coating material. In addition to these components, pigment components such as color pigments, extender pigments, and special pigments (rust preventive pigments, luminescent pigments, etc.) are usually added as one component of the coating film forming material. Examples of the natural resin-based, synthetic resin-based, or rubber derivative-based vehicle used as the coating film-forming main element include those described in the method of immersing and fixing in the fishnet. Also,
Examples of the plasticizer used as a film forming subelement include tributyl phosphate, tricresyl phosphate, dibutyl fumarate, dioctyl phthalate, dibutyl maleate and the like. Further, as the surfactant used as a coating film forming subelement, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene polyoxypropylenes, sorbitan fatty acid esters, alkyl trimethyl ammonium salts, alkyl betaines Etc. can be mentioned. Further, examples of the solvent or diluent as the film-forming aid include water, alcohol, xylene, kerosene, methyl isobutyl ketone, butyl acetate, dimethylformamide, methyl cellosolve, butyl cellosolve and the like. Examples of the pigment component include talc, titanium white, yellow lead, navy blue, rouge, phthalocyanine blue, and various inorganic or organic pigments other than these. When using each component as the coating film forming material,
It is possible to select and blend one or more species.

In the method of adding a small amount of the vanillylamine derivative to the seawater cooling water system as described above, a 5 to 50% solution of the active ingredient is proportionally injected to the cooling water at a ratio of 1 to 50 ppm. In addition, in the method of fixing to fishnets and other objects as described above and above, the type of the object, the coating method (brushing, spraying, dipping method, etc.), the storage period, the storage method, etc. are taken into consideration in the application. It is determined so that the physical properties of the paint and the coating film will be suitable. Usually, the coating film forming material is mixed in an amount of 99 to 50 parts by weight with respect to 1 to 50 parts by weight of one or more kinds of the active ingredients of the present invention. More specifically, 10 to 30 parts by weight of one or more of the active ingredients,
As a coating film forming material, 10 to 40 parts by weight of a coating film forming main element, 5 to 65 parts by weight of a coating film forming sub-element, and a coating film forming auxiliary element 0 to 65
Parts by weight, and 0 to 40 parts by weight of the pigment component are blended.
Further, it may be used in combination with another anti-adhesion agent within a range where there is no toxicity or environmental pollution.

[0015]

EXAMPLES Examples of the present invention will be shown below.

[Test 1] The paint of Example 1 and the paint of Comparative Example 1 having the formulations shown in Table 1 were prepared and applied on the surface of each test piece. Then, after 6 months and 12 months after each test piece was installed in the alley in seawater, the state of adhesion of marine organisms (blue mussel, barnacles, magnolia japonicus) was observed, and the results are shown in Table 1. Further, the same test was conducted on the test piece (blank) to which nothing was applied, and the results are also shown in Table 1.

[0017]

[Table 1]

[Test 2] Polyvinyl chloride 100 × 10
A test plant was prepared in which a test piece (cedar board) was placed in a 0 mm square and 2.5 m long canal, and the flow rate was 7.5 in this canal.
Seawater was passed under the conditions of m ³ / hr and a flow velocity of 0.35 m / sec. Then, the additives of Examples 2 and 3 and the additive of Comparative Example 2 having the composition and the addition conditions shown in Table 2 were added to the seawater, respectively, and the marine organisms (blue mussel,
The adhesion amount of barnacles) was examined, and the results are shown in Table 2.
Further, the same test was conducted for the case where nothing was added (blank), and the results are also shown in Table 2.

[0019]

[Table 2]

[Test 3] A solution of Example 4 having the composition shown in Table 3 and a solution of Comparative Example 3 were prepared, and a polyethylene knotless net (6 sections, 400 denier / 60 pieces) was added to each of the above coating materials. After soaking, it was air dried. Then, each of the above test nets is dipped and maintained in seawater at a depth of 1 m below sea level for 3 months (from April to
The state of adhesion of marine organisms to the net in July) was observed, and the results are shown in Table 3.

[0021]

[Table 3]

[0022]

INDUSTRIAL APPLICABILITY As described above, the anti-adhesion agent for marine organisms of the present invention does not kill the marine organisms by the vanillylamine derivative which is the active ingredient, but since it has excellent repellent effect, it is a barnacle or mussel. It is possible to prevent marine organisms such as those from attaching to fishing nets, ship bottoms, marine intake channel walls, and the like. Therefore, it can be used, for example, in various plants such as thermal power plants and steel mills to prevent functional deterioration of the cooling water system, and also in aquaculture and fisheries and ships, various damages and functions caused by the adhesion of marine organisms. It is possible to prevent the decrease.

The vanillylamine derivative used in the present invention has a high level of safety for human livestock and fish, as well as the environment, as is clear from the fact that vanillyl nonylamide is extracted from mustard. is there.

Claims (1)

[Claims] 1. A general formula: An agent for preventing adhesion of marine organisms, which comprises, as an active ingredient, one or more vanillylamine derivatives represented by.