JPH08231898A - Underwater antifouling composition - Google Patents

Abstract

PURPOSE: To obtain an underwater antifouling compsn. for preventing the deposition of marine life to the surfaces of a ship, the underwater portion of a marine construction, a head race pipe in a power plant, a fishing net, etc. CONSTITUTION: The compsn. comprises as the main components a hydrophobic silicone oil having a contact angle of at least 50 deg. with water and a weakly hydrophilic silicone oil having a contact angle of at least 10 deg. and less than 50 deg. with water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater antifouling composition for preventing marine organisms from adhering to the surfaces of ships, submerged parts of marine structures, water conduits of power plants, fishnets and the like.

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Ships,
For bridges, offshore tanks, underwater structures such as buoys, power conduits for power plants, aquaculture columns used for seafood culture, fish nets, set nets, etc. , Various kinds of marine organisms such as cracks adhere. Due to the adhesion of these marine organisms, the traveling speed of the ship decreases, fuel efficiency deteriorates, and fuel cost increases. In the headrace pipe of the power plant, the pipe is blocked and the base material is eroded. In the net cage, the mesh is clogged by the attached organisms, and the poor circulation of seawater causes a large amount of death of cultured fish.

As a method for preventing the adhesion of marine organisms, an underwater antifouling composition containing a metal compound such as a copper compound or an organic tin compound as a main component has been used.
However, these metal compounds accumulate in fish and shellfish, and there is a concern that they will adversely affect the human body eating them. In addition, since it has a strong irritating odor and toxicity, there is concern about the influence on the body of the worker when using the underwater antifouling composition.

For this reason, the underwater antifouling composition is highly safe against seafood and the human body, has a sufficient anti-adhesion effect against marine adherent organisms, and has a longer duration of anti-adhesion effect. The development of products has been demanded, and recently, the use of underwater antifouling agents for metal compounds has been regulated. Therefore, it has been changed to safe underwater antifouling compositions containing no metal compounds. From this point of view, various underwater antifouling agents have been proposed in the past. In particular, many underwater antifouling agents using a silicone-based resin have been proposed, for example, a reaction-curable silicone resin and R _x Si (R'OH). ) Agent comprising a hydroxyl group-containing silicone resin represented by _y O _{(4-xy) / 2} and having a molecular weight of 250 to 200,000 (JP-A-62-252480), a reaction-curable silicone resin and R _x Si ( R'X) _y O
_{(4-xy) / 2} polar group-containing silicone resin and consisting agent (JP 63-43973 JP), the reaction curable silicone resin and _{R x Si (ROR) y O} (4-xy) / 2 in the silicone An agent comprising a resin (JP-A-3-255169), an agent in which an oxyalkylene group-containing organopolysiloxane having an HLB in the range of 3 to 12 is mixed with a film-forming resin (JP-A-3-20370), A mixture of a room temperature curable silicone rubber and a polyoxyalkylene-containing organopolysiloxane having an HLB in the range of 2 to 10 (JP-A-4-142373) and the like have been reported. By keeping the highly effective silicone oil in silicone rubber, silicone varnish, acrylic resin, melamine resin, and polyester resin, antifouling effect in water is achieved. It is intended to formed.

However, when using an underwater antifouling agent, generally, the underwater antifouling agent is applied on a coating substrate, dried in the atmosphere and then immersed in water. Even if the agent has excellent properties, for example, an agent using a curable resin such as silicone rubber or acrylic resin cannot be expected to have the antifouling effect of the resin itself, and the silicone oil present on the surface of the resin may flow into water. When the amount decreases along with it, biofouling begins to occur on the surface of the curable resin, and biofouling cannot be suppressed.

The present invention has been made in view of the above circumstances.
An object of the present invention is to provide an underwater antifouling composition capable of holding a silicone oil having an excellent antifouling effect on a substrate for a long period of time without using another silicone oil holder such as a curable resin. .

[0007]

Means and Action for Solving the Problems The present inventors have
As a result of diligent studies to achieve the above object, silicone oil, which has been generally considered to be difficult to retain on a coating base for a long period of time because of its high fluidity, has a hydrophobicity with a contact angle with water of 50 ° or more. By combining a hydrophilic silicone oil and a weakly hydrophilic silicone oil having a contact angle with water of 10 ° or more and less than 50 °, an underwater antifouling agent using a conventional mixed composition of a curable resin and silicone oil can be used. Also has a great holding power for silicone oil,
It was found that a good antifouling effect can be maintained for a long period of time, and the present invention has been completed.

Therefore, according to the present invention, the contact angle to water is 5
An underwater antifouling composition comprising a hydrophobic silicone oil of 0 ° or more and a weakly hydrophilic silicone oil having a contact angle to water of 10 ° or more and less than 50 ° as main components.

The present invention will be described in more detail below. The underwater antifouling composition of the present invention contains a hydrophobic and weakly hydrophilic silicone oil as a main component. In this case, the hydrophobic silicone oil having a contact angle with water of 50 ° or more, preferably 50 to 105 ° is used.

Specific examples of the hydrophobic silicone oil include polydimethyl silicone oil, epoxy-modified silicone oil, amino-modified silicone oil, fluorine-modified silicone oil, and mercapto-modified silicone oil, which are conventionally known as antifouling substances in water. Can be mentioned.

On the other hand, as the weakly hydrophilic silicone oil, one having a contact angle with water of 10 ° or more and less than 50 °, more preferably 30 ° or more and 50 ° or less is used. If a silicone oil having a contact angle of less than 10 ° is used, it becomes easily soluble in water and the antifouling effect is reduced. Specific examples of the weakly hydrophilic silicone oil include carbinol modified silicone oil, polyether modified silicone oil, hydrophilic special modified silicone oil, higher fatty acid ester modified silicone oil, carboxyl modified silicone oil and phenol modified silicone oil. Can be mentioned.

The combined ratio of the hydrophobic silicone oil and the weakly hydrophilic silicone oil is 10: 9 by weight.
It is preferably in the range of 0 to 90:10, particularly preferably in the range of 30:70 to 80:20, and if it is out of the above range, the antifouling effect may decrease.

The underwater antifouling composition of the present invention mainly comprises a hydrophobic silicone oil having a contact angle with water of 50 ° or more and a weakly hydrophilic silicone oil having a contact angle with water of 10 ° or more and less than 50 °. Although it is used as a component, its form is such that even if this mixture is used as it is, paint, solution,
It may be prepared in the form of an emulsion or the like. When the composition is adjusted to a paint, solution, emulsion or the like, it is preferable to adjust the content of the mixture to be 1% by weight or more, especially 10 to 50% by weight. Examples of the solvent include benzene, toluene, xylene, methanol, methyl acetate, methyl ethyl ketone, acetone, and 1-methoxy-2-propanol. The amount of these solvents used is not particularly limited. Further, if necessary, a surfactant, a thickener, a plasticizer, a coloring pigment, an extender pigment, a physiologically active substance agent, an anti-sagging agent, etc., which are usually used in paints, can be blended, and an underwater antifouling composition can be added. An underwater antifouling composition suitable for the substrate can be obtained by determining the blending amount of these depending on the place of use and the like.

The method of using the underwater antifouling composition of the present invention is not particularly limited, and it can be applied as a paint, or by a method such as dipping treatment, underwater structures such as ships, bridges, offshore tanks and buoys, and power plants. The aqueducts, aquaculture struts used for aquaculture, fishnets, stationary nets, etc. can be treated. The material of the target fishnet is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, silk, and wool, polyvinyl chloride, polyvinylidene chloride, polyfluorinated ethylene, polyamide, polyethylene, polypropylene, polystyrene, polyacrylonitrile. It can be applied to fish nets made of synthetic fibers such as.

The amount of the underwater antifouling composition of the present invention to be used is not particularly limited, but is 5 to 10 g / m ² as a dry weight for the construct to be treated and 5 for a fish net.
It is generally about 30% by weight.

[0016]

According to the underwater antifouling composition of the present invention, it is possible to exert a sufficient anti-adhesion effect against marine fouling organisms, and further, the anti-adhesion effect is sufficiently long-lasting, that is, vessels, bridges and marine tanks. It is possible to effectively prevent marine organisms from adhering to undersea structures such as, aquaculture columns, fishnets, and fixed nets.

Further, according to the underwater antifouling composition of the present invention,
Since it can be used by directly coating it on a substrate without using a silicone oil holder such as another curable resin, it is excellent in convenience.

[0018]

EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples 1 to 4, Comparative Examples 1 to 16] Table 1,
An underwater antifouling composition having the formulation shown in 2 was prepared. Next, after immersing the fishnet in each of the underwater antifouling composition, take out,
This was air-dried for 18 hours for antifouling treatment. The 400 × 200 mm fish net thus antifouling-treated was attached to a stainless steel frame and hung in the sea at a depth of 1.5 m. The fishnet immersed in the seawater was pulled up every month to observe the state of attachment of organisms, and evaluated according to the following criteria. 1; No organism attached. 2; A small amount of organisms are partially attached. 3; A small amount of organisms are attached overall. 4; The organisms are considerably attached overall. Moreover, the contact angle with respect to water is FACE contact angle meter CA-S1.
The measurement was performed by a droplet method using a 50 type (manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Tables 3 and 4.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

[0023]

[Table 4]

[0024]

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[0025]

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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masayoshi Tanaka 2-6-1, Otemachi, Chiyoda-ku, Tokyo Shin-Etsu Chemical Co., Ltd. (72) Inventor Atsushi Miyaji 1-5, Uchikanda, Chiyoda-ku, Tokyo 13 Shin-Etsu Astec Co., Ltd.

Claims (2)

[Claims] 1. An underwater antifouling composition comprising a hydrophobic silicone oil having a contact angle with water of 50 ° or more and a weakly hydrophilic silicone oil having a contact angle with water of 10 ° or more and less than 50 ° as main components. . 2. A weight ratio of a hydrophobic silicone oil having a contact angle to water of 50 ° or more to a weakly hydrophilic silicone oil having a contact angle to water of 10 ° to less than 50 ° is 10:90 to 90:10. The underwater antifouling composition according to claim 1, which is within the range.