JPH0912413A - Aquatic antifouling agent - Google Patents

Abstract

PURPOSE: To obtain an antifouling agent exhibiting sufficient adhesion preventing effect on fouling marine organisms, sufficiently continuing the adhesion preventing effect and capable of effectively preventing the adhesion of marine life to a ship, a marine construction such as bridge and marine tank and cultivation post, fishing net, fixed shore net, etc. CONSTITUTION: This antifouling agent is composed mainly of a mixture of (A) a composition produced by reacting or mixing a hydrophobic silicone oil having a contact angle of >=50 deg. to water with a coupling agent and (B) a weakly hydrophilic silicone oil having a contact angle of >=10 deg. and <50 deg.. The weight ratio of the component A to the component B is preferably within the range of 10:90 and 90:10.

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 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,
Bridges, offshore tanks, underwater structures such as buoys, water conduits for power plants, aquaculture columns used for aquaculture, fishnets, set nets, etc. include barnacles, algae, bivalves, squirts, hemlocks, magnolias, A wide variety of marine organisms such as sea anemones and cracks adhere. The adhesion of these marine organisms causes a decrease in the traveling speed of the ship, and fuel cost increases to maintain the speed. In addition, 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 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 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 effect on the body of workers when using an underwater antifouling agent.

Therefore, the underwater antifouling agent is highly safe against seafood and humans, has a sufficient anti-adhesion effect against marine adherent organisms, and has a longer duration of anti-adhesion effect. Has been demanded and the use of underwater antifouling agents of metal compounds has been regulated recently, and therefore safer underwater antifouling agents containing no metal compounds have been used.

From this point of view, various conventional underwater antifouling agents have been used.
Proposed, but especially in water using silicone resin
There are many proposals for antifouling agents, such as reaction-curable silicone.
Resin and R_xSi (R'OH)_yO_{(4-xy) / 2}Represented by
Hydroxyl group-containing silicone resin having a molecular weight of 250 to 200,000
An agent consisting of a fat (JP-A-62-252480),
Reaction-curable silicone resin and R_xSi (R'X)_yO
_{(4-xy) / 2}From polar group-containing silicone resin represented by
Agent (JP-A-63-43973), reaction curing type
Silicone resin and R_xSi (ROR )_yO_{(4-xy) / 2}Shi
Agent composed of silicone resin (JP-A-3-255169)
Gazette), HLB in the film-forming resin is in the range of 3 to 12.
Chain-shaped organopolysiloxane containing oxyalkylene groups
Mixed agent (JP-A-3-20370), room temperature curing
Silicone rubber and poly with HLB in the range of 2-10
Mixing with oxyalkylene-containing organopolysiloxane
(Japanese Patent Laid-Open No. 4-142373), etc. have been reported.
In any case, these are silicone rubber and silicone.
Corn varnish, acrylic resin, melamine resin, polys
By retaining it in tellurium, etc., the antifouling effect in water
To achieve.

However, when an underwater antifouling agent is used, generally, the underwater antifouling agent is applied onto a coating substrate, dried in the atmosphere and then immersed in water. Even if the agent has excellent properties, for example, an underwater antifouling 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 this surface flows into water. When it is decreased along with the above, biofouling starts to occur on the surface of the curable resin, and biofouling cannot be suppressed.

[0007] The present invention has been made in view of the above circumstances,
An object of the present invention is to provide an underwater antifouling agent capable of holding 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.

[0008]

Means and Action for Solving the Problems The present inventors have
In order to achieve the above object, silicone oil, which has been generally considered to be difficult to hold on a coating base for a long time due to its high fluidity, is treated with a hydrophobic silicone oil having a contact angle with water of 50 ° or more and water. Contact angle is 10 °
By using a combination with a weakly hydrophilic silicone oil having a temperature of less than 50 °, the silicone oil retainability is greater than that of the conventional underwater antifouling agent of a mixed composition of a curable resin and a silicone oil. We proposed an underwater antifouling agent that can obtain an antifouling effect. Based on this proposal, the present inventors further conducted diligent studies to obtain an underwater antifouling agent capable of maintaining a good antifouling effect for a long period of time, and as a result, the hydrophobicity with a contact angle with water of 50 ° or more was obtained. It has an excellent antifouling effect on an underwater antifouling agent in which an appropriate amount of a composition obtained by reacting or mixing a silicone oil with a coupling agent and a weakly hydrophilic silicone oil having a contact angle with water of 10 ° or more and less than 50 ° is blended. I found out.

That is, a composition obtained by reacting or mixing a coupling agent with a hydrophobic silicone oil having a contact angle with water of 50 ° or more and a contact angle with water of 10 ° or more 50
An underwater antifouling agent in which an appropriate amount of a weakly hydrophilic silicone oil having a degree of less than 0 ° is blended is a mixed antifouling agent and a hydrophobic agent of the above curable resin and silicone oil due to the synergistic effect of the three components constituting the underwater antifouling agent. The present invention has been found to have a larger holding power for silicone oil than a composition in which a hydrophilic silicone oil and a weakly hydrophilic silicone oil are mixed, and to maintain a good antifouling effect for a long period of time, and have completed the present invention. .

Therefore, according to the present invention, (A) a composition in which a coupling agent is reacted or mixed with a hydrophobic silicone oil having a contact angle with water of 50 ° or more, and (B) a contact angle with water of 10 ° or more. Provided is an underwater antifouling agent whose main component is a mixture with a weakly hydrophilic silicone oil having an angle of less than 50 °. In this case, the weight ratio of the component (A) and the component (B) is preferably within the range of 10:90 to 90:10.

The present invention will be described in more detail below. The underwater antifouling agent of the present invention has a contact angle with water of 50 °.
The composition obtained by reacting or mixing the coupling agent with the above hydrophobic silicone oil has a contact angle of 10 ° with water.
The main component is a mixture with a weakly hydrophilic silicone oil having a temperature of less than 50 °. Examples of the hydrophobic silicone oil having a contact angle with water of 50 ° or more include polydimethyl silicone oil, epoxy-modified silicone oil, amino-modified silicone oil, fluorine-modified silicone oil, mercapto-modified silicone oil and the like.

As the coupling agent, vinyltrichlorosilane, vinyl (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ
-Methacryloxypropyltrimethoxysilane, β-
(3,4 Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyl Dimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane,
Examples thereof include silazane and titanate. In this case, the reaction or mixing ratio of the hydrophobic silicone oil and the coupling agent is 100: 0.1 to 100: 1 as a weight ratio.
A range of 0, particularly a range of 100: 0.5 to 100: 2 is preferable.

Next, as the weakly hydrophilic silicone oil, a weakly hydrophilic silicone oil having a contact angle with water of 10 ° or more and less than 50 ° is used. If a weakly hydrophilic silicone oil having a contact angle with water of less than 10 ° is used, it becomes easily soluble in water and the antifouling effect is reduced. Here, as the weakly hydrophilic silicone oil having a contact angle with water of 10 ° or more and less than 50 °, specifically, carboxyl-modified silicone oil, carbinol-modified silicone oil, polyether-modified silicone oil, amino-modified silicone oil, phenol Modified silicone oil etc. can be mentioned. In this case, the compounding ratio of the composition obtained by reacting or mixing the hydrophobic silicone oil with the coupling agent and the weakly hydrophilic silicone oil is in the range of 10:90 to 90:10 by weight, particularly 30:70.
It is preferably in the range of 80:20, and if it is out of the above range, the antifouling effect may decrease.

The underwater antifouling agent of the present invention has a contact angle to water of 1 with a composition obtained by reacting or mixing a coupling agent with a hydrophobic silicone oil having a contact angle to water of 50 ° or more.
The main component is a mixture with a weakly hydrophilic silicone oil of 0 ° or more and less than 50 °, and the form may be the mixture as it is or the form adjusted to a paint, solution or emulsion. . 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. As the solvent, benzene, toluene, xylene, methanol, ethyl acetate, methyl ethyl ketone, acetone,
1-methoxy-2-propanol etc. can be mentioned. Furthermore, if necessary, surfactants, thickeners, plasticizers, coloring pigments, extender pigments, physiologically active substances, anti-sagging agents, etc., which are usually used in paints, can be blended, and use of an underwater antifouling agent is possible. An underwater antifouling agent suitable for the substrate can be obtained by determining the blending amount of these depending on the location and the like.

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 method such as dipping treatment, underwater structures such as ships, bridges, offshore tanks and buoys.
It is possible to treat water pipes of power plants, aquaculture columns used for aquaculture, fishnets, stationary nets, and the like. The material of the target fishnet is not particularly limited, and for example, cotton,
It can be applied to a fish net made of natural fibers such as hemp, silk and wool, and synthetic fibers such as polyvinyl chloride, polyvinylidene chloride, polyfluoroethylene, polyamide, polyethylene, polypropylene, polystyrene and polyacrylonitrile.

[0016]

EFFECTS OF THE INVENTION The underwater antifouling agent of the present invention can exert a sufficient anti-adhesion effect against marine fouling organisms, and further has sufficient sustainability of the anti-adhesion effect, and can be used for ships, bridges, marine tanks, etc. It is possible to effectively prevent marine organisms from adhering to undersea structures, aquaculture columns, fishnets, set nets, and the like.

Further, the underwater antifouling agent of the present invention is excellent in simplicity because it can be used by directly coating it on a substrate without using a silicone oil holder such as another curable resin. It is a thing.

[0018]

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. The contact angle of each silicone oil is F
ACE contact angle meter CA-S150 type (Kyowa Interface Science Co., Ltd.)
Was measured by the droplet method.

[Examples 1 to 6, Comparative Examples 1 to 9] Tables 1 and 2
An underwater antifouling agent having the formulation shown in was prepared. Next, after immersing the fishnet in each of the underwater antifouling agents, take it out and remove it.
It was air-dried for an hour and then treated for antifouling. Antifouling treated in this way 4
A 00 × 200 mm fish net 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. The results are shown in Tables 3 and 4. 1; organisms are not attached at all. 2; A small amount of organisms are partially attached. 3: A small amount of organisms are attached as a whole. 4: The organism is quite attached as a whole.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

[0023]

[Table 4]

* 1 Epoxy-modified silicone oil having a contact angle to water of 74 ° and an epoxy group equivalent of 350 (25
Viscosity at ℃ 2000cs)

[0025]

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* 2 Polydimethyl silicone oil having a contact angle with water of 103 ° (viscosity 3000c at 25 ° C.
s)

[0027]

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* 3 γ-aminopropyltriethoxysilane H ₂ NC ₃ H ₆ Si (OC ₂ H ₅ ) ₃

* 4 N-β (aminoethyl) γ-amino
Propylmethyldimethoxysilane H_TwoNC_TwoH_FourNHC_ThreeH₆Si (OC H_Three)_Three

* 5 Carbinol-modified silicone oil with a contact angle to water of 39 ° (viscosity 125c at 25 ° C.
s)

[0031]

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* 6 Polyether-modified silicone oil having a contact angle to water of 26 ° (viscosity 140c at 25 ° C.
s)

[0033]

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* 7 Polyether-modified silicone oil having a contact angle with water of 3 ° (viscosity of 100 cs at 25 ° C)

[0035]

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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. A composition comprising (A) a composition obtained by reacting or mixing a coupling agent with a hydrophobic silicone oil having a contact angle with water of 50 ° or more, and (B) having a contact angle with water of 10 °.
An underwater antifouling agent whose main component is a mixture with a weakly hydrophilic silicone oil having a temperature of not less than 50 °. 2. The weight ratio of the component (A) and the component (B) is 1
The underwater antifouling agent according to claim 1, which is in the range of 0:90 to 90:10.