JPH08193174A - Underwater antifouling agent - Google Patents

Abstract

PURPOSE: To obtain an underwater antifouling agent which is highly safe for fishes, shellfishes, and human bodies and has excellent effects on preventing the adhesion of marine organisms by using as the main component a mixture comprising a specific resin and a specific silicone resin. CONSTITUTION: A mixture comprising a resin (A) selected from among epoxy, alkyd, amino, acrylic, methacrylic, polyurethane, polyester, xylene. phenol, toluene, and styrene resins and a silicone resin (B) having groups formed by the addition reaction of a triglycerin monoallyl ether represented by the formula (wherein R<1> is a 3-10C monovalent hydrocarbon group having a terminal allyl group) to the side chains or molecular terminals is used as the main component. The mixing ratio of component A to Component B is pref. (99:1)-(10:90), still pref. (95:5)-(60:40).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater antifouling agent that prevents marine organisms from adhering to the surfaces of ships, submerged parts of marine structures, water conduits of power plants, fishing nets and the like.

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Ships,
For bridges, offshore tanks, marine structures such as buoys, power conduits for power plants, aquaculture columns used for aquaculture, fishing nets, set nets, etc. A wide variety of marine organisms such as sea anemones and cracks adhere. Adhesion of these marine organisms causes a decrease in traveling speed, an increase in fuel cost and corrosion of the ship bottom in ships, and blockages and corrosion in the headrace pipes of power plants. The mesh is clogged by the attached organisms, and the poor circulation of seawater causes large-scale killing of cultured fish.

As a method for preventing the adhesion of marine organisms, an underwater antifouling agent 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 eating them will adversely affect the human body. Furthermore, due to its strong irritating odor and toxicity, there is concern about adverse effects on the body of workers when using an underwater antifouling agent.

For this reason, the development of an underwater antifouling agent which is highly safe for fish and shellfish and humans, can exert a sufficient anti-adhesion effect against marine adherent organisms, and has a sufficiently long lasting anti-adhesion effect In particular, recently, since the regulation of the use of a metal compound in an underwater antifouling agent, it has been changed to a safer underwater antifouling agent containing no metal compound,
Many proposals have been made for an underwater antifouling agent using a silicone resin, and it is known that a silicone resin partially having a hydrophilic functional group has an effect of preventing adhesion of marine organisms, but it is safer. A highly effective underwater antifouling agent is desired.

The present invention has been made in view of the above circumstances and is highly safe for seafood and the human body, has a sufficient anti-adhesion effect for marine adherent organisms, and has a duration of the anti-adhesive effect. The purpose is to provide a sufficiently long underwater antifouling agent.

[0006]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventor diligently studied the effect of preventing adhesion of marine organisms to silicone resins containing various hydrophilic functional groups, and as a result, The present inventors have found that a mixture of a silicone resin to which triglycerin monoallyl ether represented by the following general formula (1) is added and the following resin has a remarkable antifouling effect, and have completed the present invention.

Therefore, the present invention provides epoxy resin, alkyd resin, amino resin, acrylic resin, methacrylic resin,
Polyurethane resin, polyester resin, xylene resin,
Underwater protection containing a mixture of a resin selected from a phenol resin, a toluene resin and a styrene resin and a silicone resin having triglycerin monoallyl ether represented by the following general formula (1) added to its side chain or terminal. Providing a soiling agent.

[0008]

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The reason why the above triglycerin monoallyl ether-added silicone resin has an excellent antifouling effect in water is not always clear, but this triglycerin monoallyl ether-added silicone resin is a base material in seawater. While the hydrophobic polysiloxane chain adheres to the upper part, the hydrophilic glycerin site is placed on the side in contact with seawater, and the biological action is prevented by the synergistic action of the glycerin site's swaying motion and the unique lubricity of silicone. It is considered that Furthermore, by adding the above resin to the silicone resin to which the triglycerin monoallyl ether having excellent antifouling effect is added, the dissolution rate of the silicone resin to which triglycerin monoallyl ether is added from the coating film base into seawater is significantly increased. Because it will be late
It is considered that the excellent antifouling effect of the silicone resin to which the triglycerin monoallyl ether is added can be maintained for a long period of time.

The present invention will be described in more detail below. The underwater antifouling agent of the present invention is a silicone obtained by adding a specific resin and triglycerin monoallyl ether represented by the following general formula (1) to a side chain or terminal. It is mainly composed of a mixture with a resin.

[0011]

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Here, the specific resin is an epoxy resin, an alkyd resin, an amino resin, an acrylic resin, a methacrylic resin, a polyurethane resin, a polyester resin, a xylene resin, a phenol resin, a toluene resin, or a styrene resin. The seeds may be used alone or in combination of two or more.

On the other hand, the silicone resin mixed with these resins has the triglycerin monoallyl ether of the above formula (1) added to the terminal or side chain.

In this case, the silicone resin to which the triglycerin monoallyl ether is added is not limited, and may have a chain structure, a branched chain structure or a network structure.
Hydrogen atom (SiH group) bonded to silicon atom in one molecule
An organohydrogenpolysiloxane having at least one is used, and the C—C double bond of triglycerin monoallyl ether is added to its SiH group. The addition reaction can be performed by a known method. Typically, the organopolysiloxane represented by the following general formula (2) is preferably used.

[0015]

[Chemical 4]

[0016]

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In the above general formula (2), n and m are integers of 0 or more, and in particular, the viscosity at 25 ° C. is 0.65 to 10
00000cs, preferably 100 to 100000cs
Indicates the number.

Here, the mixing ratio of the resin and the silicone resin to which the triglycerin monoallyl ether is added is preferably in the range of 99: 1 to 10:90, more preferably in the range of 95: 5 to 60:40. Is preferred.

The underwater antifouling agent of the present invention may be used as it is, or may be prepared in the form of paint, solution, emulsion or the like. When the composition is prepared as a paint, solution, emulsion, etc., it is preferable to prepare such a mixture so as to contain 1% by weight or more, particularly 10 to 50% by weight. If necessary, the underwater antifouling agent according to the present invention may contain a thickener, a plasticizer, a coloring pigment, a moisture resistant pigment, a physiologically active substance, a surfactant, an anti-sagging agent, etc., which are usually used in paints. It is possible, and the kind and amount thereof are not particularly limited.

As the solvent, it is preferable to use benzene, toluene, xylene, methanol, ethyl acetate, methyl ethyl ketone, acetone, 1-methoxy-2-propanol and the like.

The method of using the underwater antifouling agent of the present invention is not particularly limited, and it may be applied as a paint or by a dipping treatment, for example, underwater structures such as ships, bridges, offshore tanks and buoys, and power plants. Can be used to process aqueducts, aquaculture struts used for aquaculture, fishing nets, set nets, and the like. There are no particular restrictions on the material of the target fishing net,
For example, natural fibers such as cotton, linen, silk, wool, polyvinyl chloride, polyvinylidene chloride, polyethylene fluoride,
It can be applied to fishing nets made of synthetic fibers such as polyamide, polyethylene, polypropylene, polystyrene, polyacrylonitrile and the like.

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

[0023]

INDUSTRIAL APPLICABILITY According to the underwater antifouling agent of the present invention, it is highly safe for fish and shellfish and humans, can exert a sufficient anti-fouling effect on marine fouling organisms, and has a long term antifouling effect Therefore, it is possible to effectively prevent marine organisms from adhering to underwater structures such as ships, bridges and offshore tanks, aquaculture columns, fishing nets, and fixed nets.

[0024]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

First, an underwater antifouling agent having each composition shown in Table 1 was prepared, and a fishing net (400 × 200 mm) was immersed in each underwater antifouling agent for about 10 minutes. After that, each fishing net was taken out and air dried for 18 hours (antifouling treatment). Next, the antifouling-treated fishing net was attached to a stainless steel frame and hung in the sea at a depth of 1.5 m.

Evaluation The fishing net immersed in the seawater was pulled up every month to observe the state of adhesion of marine organisms. In addition, the evaluation of the adhesion status of marine organisms was performed according to the following criteria. Table 2 shows the results. 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.

[0027]

[Table 1]

[0028]

[Chemical 6]

[0029]

[Table 2]

From the results shown in Table 2, the underwater antifouling agent of the present invention (Examples 1 to 8) can remarkably prevent the adhesion of marine fouling organisms, and the persistence of the antifouling effect can be maintained for a long time. Was recognized.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location C09K 3/00 112 F (72) Inventor Masayoshi Tanaka 2-6-1, Otemachi, Chiyoda-ku, Tokyo Shin-Etsu Chemical Co., Ltd. (72) Inventor Atsushi Miyaji 1-5-13 Uchikanda, Chiyoda-ku, Tokyo Shin-Etsu Astec Co., Ltd. (72) Inventor Mitsuo Asai 1 Hitomi, Otomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (1)

[Claims] 1. A resin selected from an epoxy resin, an alkyd resin, an amino resin, an acrylic resin, a methacrylic resin, a polyurethane resin, a polyester resin, a xylene resin, a phenol resin, a toluene resin and a styrene resin, and a compound represented by the following general formula (1): ) [Chemical 1] An underwater antifouling agent whose main component is a mixture with a silicone resin having a triglycerin monoallyl ether added to the side chain or terminal shown by.