JPH06172682A - Underwater antifoulant - Google Patents

Abstract

PURPOSE:To obtain the subject underwater antifoulant capable of continuously preventing adhesion of marine organisms to water-immersed part of ships and marine structures, fishing nets, etc., by containing an epoxy-modified silicone resin having a specific epoxy equivalent. CONSTITUTION:The objective underwater antifoulant consists of an epoxy- modified silicone resin containing one or more epoxy groups in one molecule and having preferably 1000-5000 epoxy equivalent {e.g. a compound expressed by the formula [R<1> is monovalent hydrocarbon such as 1-8C alkyl or alkenyl; R<1> to R<4> are monovalent hydrocarbon such as 1-8C alkyl or 1-8C alkenyl or epoxy group-containing organic group such as glycidoxyalkyl, with proviso that at least one thereof is epoxy group-containing organic group; m and n are integer of >=0]}. Furthermore, the viscosity of the epoxy-modified silicone resin is especially preferably 1000-10000cs (at 25 deg.C).

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 for preventing marine organisms from adhering to ships, submerged parts of marine structures, fishnets and the like.

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Ships,
Submarine structures such as bridges and offshore tanks, struts for aquaculture, fishnets, set nets, etc. are barnacles, algae, bivalves, ascidians, hemlock beetles, sea anemones, magnolias,
A wide variety of marine organisms such as Collembola are attached. If such marine organisms adhere, the navigation speed of ships and undersea structures will decrease and the corrosion will occur, and the nets will block the meshes, resulting in large-scale lethality of fish due to poor circulation of seawater.

As a method for preventing the attachment of marine organisms, a method using a heavy metal compound such as a copper compound or an organic tin compound is known. In addition, N-arylmaleimides as non-heavy metal compounds (JP-A-53-932).
No. 0, JP-A-55-40608), benzanilides (JP-B-62-41493), polyaminomonocarboxylic acid compounds (JP-A-61-140501), silane compounds (JP-A-3-20286). Japanese Patent Laid-Open No. Hei 3-20370) and the like are known.

However, since copper compounds and organotin compounds have strong irritation and toxicity, they have a handling problem in antifouling treatment, and seawater is contaminated, which may affect seafood and human bodies. I am worried. On the other hand, the non-heavy metal compound has a problem that, even if its safety is confirmed, it cannot exert a sufficient effect against various marine fouling organisms due to its narrow action spectrum, or its sustainability is weak.

Therefore, it is highly safe for fish and shellfish, has a sufficient anti-adhesion effect against marine fouling organisms, and has a sufficient sustainability of the anti-adhesion effect. There was a demand for the development of a soiling agent.

[0006]

Means for Solving the Problems The present inventor has made extensive studies in order to meet the above demands, and as a result, has an epoxy equivalent of 100 to 100 containing one or more epoxy groups in one molecule.
It has been found that 5000 epoxy-modified silicone resin is effective as an antifouling agent in water.

That is, such an epoxy-modified silicone resin gradually hydrolyzes in seawater and dissolves in seawater, and the antifouling agent-treated surface is always in a new state, effectively preventing the adhesion of marine fouling organisms. In addition to being able to do this, we found that this anti-adhesion effect lasts long enough, and because it is a silicone resin, it is highly safe for seafood and the human body,
The present invention has been completed.

Accordingly, the present invention provides an underwater antifouling agent characterized by containing an epoxy-modified silicone resin having an epoxy equivalent of 100 to 5000 containing one or more epoxy groups in one molecule.

The present invention will be described in more detail below. The underwater antifouling agent of the present invention has an epoxy equivalent of 100 to 100 containing one or more epoxy groups in one molecule as described above.
It contains 5,000 epoxy-modified silicone resins.

Specific examples of such an epoxy-modified silicone resin include silicone resins represented by the following formula (1).

[0011]

[Chemical 1]

In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and R ² , R ³ and R ⁴ are substituted or unsubstituted monovalent hydrocarbon groups or epoxy group-containing organic groups, respectively. , R
^At least one of ² , R ³ and R ⁴ is an epoxy group-containing organic group. In this case, the monovalent hydrocarbon group has 1 carbon atom.
The alkenyl group, the alkenyl group, the aryl group, the aralkyl group, and the like, and halogen-substituted products thereof are listed. The epoxy group-containing organic group may, for example, be a glycidoxyalkyl group, an epoxycyclohexyl group or an epoxycyclohexylalkyl group.

In addition, m and n are integers of 0 or more, and particularly, the viscosity of the epoxy-modified silicone resin is 100 to 20.
000cs, especially 1000-10,000cs (25 ° C)
The number is preferably

The epoxy-modified silicone resin used in the present invention must have an epoxy equivalent of 100 to 5000, preferably 1000 to 5000, and when the epoxy equivalent is less than 100, the epoxy modified silicone resin is used to form a fish net. When it is treated, the adhesion to the fishnet is poor and the long-term antifouling property is poor. On the other hand, if the epoxy equivalent is higher than 5000,
When immersed in seawater, the surface of the fishnet becomes a skeleton and is easily affected by fouling organisms.

The underwater antifouling agent of the present invention contains such an epoxy-modified silicone resin, and the form thereof is prepared in the form of using the silicone resin as it is or in the form of paint, solution, emulsion or the like. The form is not particularly limited as long as it contains a silicone resin containing one or more epoxy groups in one molecule and having an epoxy equivalent of 100 to 5,000. When the composition is prepared as a paint, solution, emulsion, etc., it is preferable to prepare such an epoxy-modified silicone resin in an amount of 1% by weight or more, particularly 10 to 50% by weight.

Further, as a solvent used when preparing a coating material, a solution, etc., it is preferable to use a solvent which does not react with an epoxy group, such as benzene, toluene, xylene, chloroform and the like.

Further, known antifouling agents such as bactericides and repellents can be used in combination with the underwater antifouling agent of the present invention.
Examples of such antifouling agents include aromatic halogen compounds, maleimide compounds, sulfamide compounds and the like. In this case, in particular, when an antifouling agent having a functional group reactive with an epoxide group such as an amino group or a hydroxyl group is used, the functional group gradually reacts with the epoxide group to generate alcohol, which results in seawater. Thus, the active ingredient gradually flows out, and a strong antifouling effect can be exhibited.

The method of using the underwater antifouling agent of the present invention is not particularly limited, and it can be applied as a paint or by a dipping treatment, for example, for ships, underwater structures such as bridges and offshore tanks, and props for aquaculture. , Fishnets, stationary nets, etc. can be processed. The material of the target fishnet is not particularly limited, and for example, natural fibers such as cotton, hemp, silk, and wool,
It can be applied to fish nets made of synthetic fibers such as polyvinyl chloride, polyvinylidene chloride, polyfluorinated ethylene, polyamide, polyethylene, polypropylene, polystyrene, polyacrylonitrile and the like.

The amount of the underwater antifouling agent used in the present invention is not particularly limited, but is 5 to 10 g / weight of the epoxy-modified silicone resin with respect to the construct to be treated.
It is generally about 5 to 30% by weight with respect to m ² and fish nets.

[0020]

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

The following formulas (1-a), (1-b), (1-
Using the oily epoxy-modified silicone resin shown in c) and the oily dimethylsilicone resin as a comparison, an underwater antifouling agent was prepared at the compounding ratio shown in Table 1.

[0022]

[Chemical 2]

[0023]

[Table 1]

[0024]

[Chemical 3]

With respect to each of the underwater antifouling agents prepared as described above, a fishnet was immersed therein, allowed to stand for 2 hours, then taken out, and air-dried for 18 hours to subject the fishnet to antifouling treatment.

400 × 200 m which has been thus treated to be antifouling
A fish net of m in size was attached to a stainless steel frame, hung in the sea, and kept at a water depth of 1.5 m. The fish net immersed in seawater was pulled up at regular intervals to observe the state of organism attachment. The results are shown in Table 2. In addition, in Table 2, the evaluation of the attachment state of the organisms is shown as follows. I: No organism is attached. II: A small amount of organisms are partially attached. III: A small amount of organisms are generally attached. IV: The organism as a whole is considerably attached.

[0027]

[Table 2]

[0028]

INDUSTRIAL APPLICABILITY The underwater antifouling agent of the present invention can exert a sufficient anti-adhesion effect on marine fouling organisms, and further has sufficient sustainability of the anti-adhesion effect, and can be used in the sea such as ships, bridges and marine tanks. It is possible to effectively prevent seawater organisms from adhering to structures, aquaculture columns, fish nets, fixed nets, and the like.

Front page continued (72) Inventor Minoru Takamizawa 3-2-1 Sakado, Takatsu-ku, Kawasaki-shi, Kanagawa Shin-Etsu Chemical Co., Ltd. Corporate Research Center

Claims (1)

[Claims] 1. An underwater antifouling agent comprising an epoxy-modified silicone resin having an epoxy equivalent of 100 to 5000 containing one or more epoxy groups in one molecule.