JPH11269409A - Underwater antifouling agent - Google Patents

Abstract

(57) [Summary] For 1 part by weight of a hydrophobic polymer compound,
An antifouling agent in water, comprising, as an active ingredient, an organopolysiloxane compound obtained by binding at least 2 parts by weight of a modified silicone oil having a hydrophilic functional group. [Effect] The underwater antifouling agent of the present invention can continuously exhibit an antifouling effect over a long period of time, and has no problem of environmental pollution.
It is highly safe for fish and shellfish and the human body.For example, it is applied to the surface of ships, submerged submarine structures, water pipes of power plants, fish nets, etc. It can be used effectively as a product for the purpose of prevention.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention can exert an antifouling effect continuously, and can be applied to the surface of ships, submerged structures of underwater structures, water pipes of power plants, fish nets and the like by applying them to the submarine. The present invention relates to an underwater antifouling agent capable of preventing the adhesion of organisms over a long period of time.

[0002]

2. Description of the Related Art Ships, bridges, underwater structures such as marine tanks and buoys, water supply pipes for power plants, props for cultivating fish and shellfish, fishing nets, fixed nets, and the like include barnacles, algae, bivalves, sea squirts,
Various damages occur when marine organisms such as bryozoan beetles, kanase kanashi, warekala, and marine microorganisms attach. More specifically, the running speed of a ship is reduced due to the attachment of marine organisms, so that the fuel cost increases. Clogging will occur in the headrace pipe of the power plant. In a net cage for aquaculture, clogging of the net causes poor circulation of seawater, resulting in deterioration of the quality of the fish and, in severe cases, killing of the cultured fish. In the past, to prevent such marine organisms from attaching,
A method using an antifouling agent in water using a metal compound such as an organic copper compound or an organic tin compound has been used.

However, underwater antifouling agents containing a metal compound such as an organotin compound as a main component have a high risk of causing environmental pollution. For this reason, in addition to being able to exhibit a sufficient adhesion-preventing effect on attached marine organisms, there is a demand for the development of a product that is highly safe against fish and shellfish and the human body. Furthermore, in recent years, in addition to the above-mentioned demands, since the use of organotin compounds and the like in underwater antifouling agents has been regulated, a more safe underwater antifouling agent containing no metal compounds and the like in this respect is also demanded. .

[0004] From such a viewpoint, an antifouling agent in water using a silicone resin having a hydrophilic functional group as described below has been developed and reported in recent years. (1) Reaction-curable silicone resin and R _x Si (R'O
H) The molecular weight represented by _{y O (4-xy) /} 2 250~200,0
An antifouling agent in water comprising a hydroxyl group-containing silicone resin of No. 00 (JP-A-62-252480). (2) A reaction-curable silicone resin and R _x Si (R ′
_{X) y O (4-xy} ) / 2 consisting of a polar group-containing silicone resin represented by the underwater antifouling agent (Japanese Patent No. 2503986). (3) 50 to 99% by weight of a reaction-curable silicone resin;
_{R x Si (R-OR2X)} y O (4-xy) / 2 in water antifouling composition characterized in that it contains 1 to 50 wt% silicone resin represented by (JP-A-3-255169) . (4) HL to 100 parts by weight of non-silicone film forming resin
An antifouling agent in water mixed with 1 to 50 parts by weight of an oxyalkylene group-containing linear organopolysiloxane having B in the range of 3 to 12 (Japanese Patent Publication No. 6-104793).

[0005] All of the above-mentioned underwater antifouling agents include silicone rubber, silicone varnish, acrylic resin, melamine resin,
This is a type of adding a silicone resin having a hydrophilic or polar functional group to a hydrophobic resin such as a polyester resin. A small amount of a silicone oil modified with a hydrophilic group or a polar group, which is excellent in water resistance, is held down and held.

[0006]

However, these underwater antifouling agents are excellent in the antifouling effect at the initial stage of immersion because the hydrophobic resin is a main component of the antifouling agent, but the antifouling effect is high. And there is a common problem that as the hydrophilic silicone inside the resin elutes, the hydrophobic resin becomes apparent and biofouling begins. Therefore, improvement of the sustainability of the antifouling effect has been an issue.

The present invention has been made in view of the above circumstances, and can provide an antifouling effect continuously for a long period of time. In addition, the present invention has no problem of environmental pollution, safety of fish and shellfish, and human body. The purpose is to develop an antifouling agent.

[0008]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, a hydrophilic functional group was added to 1 part by weight of a hydrophobic polymer compound. It has been found that an underwater antifouling agent containing, as an active ingredient, an organopolysiloxane compound comprising 2 parts by weight or more of a modified silicone oil bonded thereto can exert a sustained high antifouling effect and is highly safe.

That is, the present applicant considers that reducing the amount of the hydrophobic resin having a weak antifouling effect and keeping as much silicone oil having an excellent antifouling effect on the substrate as possible leads to a long-lasting antifouling effect. Antifouling agent using a mixture of a hydrophobic silicone oil and a hydrophilic silicone oil (JP-A-8-231898), 100 parts by weight of an antifouling agent in water containing a silicone resin having an oxyalkylene unit in a side chain On the other hand, there has been proposed an underwater antifouling agent (JP-A-9-296153), which comprises mixing MQ resin in a ratio of 2 to 120 parts by weight.

As a result of further studies, the present inventor has found that instead of simply mixing a hydrophobic resin and silicone oil as described above, a silicone oil having a hydrophilic group is added to a hydrophobic polymer compound. By blending the organopolysiloxane compound bound at a specific ratio as an active ingredient, the silicone oil has fluidity even in the presence of water, while being hydrophilic, and is suppressed from being eluted into water. Therefore, the hydrophilic surface is maintained for a long period of time, and an outflow prevention effect exceeding that of a mere mixture of the two components is obtained, and the antifouling effect is dramatically improved, and the effect is continuously exhibited for a long time. The present inventors have found that an underwater antifouling agent can be obtained, and have accomplished the present invention.

Accordingly, the present invention provides a method for preparing a hydrophobic polymer compound 1
Provided is an underwater antifouling agent comprising, as an active ingredient, an organopolysiloxane compound in which 2 parts by weight or more of a modified silicone oil having a hydrophilic functional group is bonded to parts by weight.

In the following, the present invention will be described in more detail. The underwater antifouling agent of the present invention comprises, as an active ingredient, an organopolysiloxane compound obtained by bonding a hydrophobic polymer compound and a modified silicone oil having a hydrophilic functional group. It is assumed that.

The type of the hydrophobic polymer is not particularly limited, but a hydrophobic resin or a hydrophobic polymer having a hydrophilic functional group partially bonded thereto is preferably used. Typical examples thereof include various silicone resins, silicone raw rubber, silicone powder, silicone gel, acrylic resin, methacrylic resin, fluororesin, polybutene resin, acrylic silicone resin, phenolic resin, polyethylene resin, various powders, and the like. . In the present invention, among these, silicone resins, specifically, MQ resins and the like are preferably used.

The modified silicone oil having a hydrophilic functional group is not particularly limited as long as it can exhibit hydrophilicity, and examples thereof include polyether-modified silicone oil and glycerin-modified silicone oil. In addition, as long as the mechanism in the present invention can be exerted and the antifouling effect can be sufficiently exerted, these resins and oils may be modified with other functional groups or the like.

The above silicone oil has a viscosity at 25 ° C. of 20 to 10,000 cs, particularly 100 to 100 cs.
5,000 cs is preferred.

In the present invention, 2 parts by weight or more, preferably 2 to 50 parts by weight, more preferably 3 to 30 parts by weight of a modified silicone oil having a hydrophilic functional group is added to 1 part by weight of the hydrophobic polymer compound. The organopolysiloxane bound by weight is incorporated. If the binding ratio of the modified silicone oil having a hydrophilic functional group is less than 2 parts by weight, it is difficult to exhibit a sufficient antifouling effect over a long period of time.

Further, there is no particular limitation on the bonding form between the hydrophobic polymer compound and the modified silicone oil having a hydrophilic functional group, and there is no particular limitation on the bonding method, and the bonding is performed by a reaction according to the compound. For example, an addition reaction, a condensation reaction and the like can be suitably employed. Specifically, a compound having an aliphatic unsaturated group, for example, an alkenyl group such as a vinyl group is used as the hydrophobic polymer compound, and a silicon-bonded hydrogen atom (ie,
A method can be employed in which a hydrophobic polymer compound and silicone oil are bonded by using a compound having a SiH group) and subjecting them to an addition reaction in the presence of an addition reaction catalyst such as a platinum catalyst. In this case, the hydrophobic polymer compound is S
The iH group and the silicone oil may have an aliphatic unsaturated group. Further, the reaction between SiH groups and SiOH groups,
A reaction between OH or SiOH and a silicon atom having an alkoxy group, an acyloxy group, or the like bonded thereto may be employed.

The underwater antifouling agent of the present invention comprises, as an active ingredient, an organopolysiloxane compound in which the above-mentioned hydrophobic polymer compound and a modified silicone oil having a hydrophilic functional group are bound, and its use form is not particularly limited. Instead, they may be used as they are, or may be prepared and used in the form of paints, solutions, emulsions, gels and the like.

In this case, when the underwater antifouling agent of the present invention is prepared in the form of a paint, a solution, an emulsion, a gel or the like, the content of the active ingredient is 1% by weight or more, especially 10 to 50% by weight in the whole preparation.
It is preferable to prepare so as to be in the range of. If the content of the active ingredient is less than 1% by weight, a satisfactory antifouling effect in water may not be obtained.

When the underwater antifouling agent of the present invention is prepared in the above-mentioned form, optional components which are usually blended in the preparation can be added as needed. Bioactive components such as bactericides, extender pigments, plasticizers,
Thickeners, surfactants, fillers, stabilizers, antioxidants,
An ultraviolet ray inhibitor, an anti-sagging agent and the like can be blended.
In addition, the addition amount of the optional component can be a normal amount as long as the effect of the present invention is not impaired.

The underwater antifouling agent of the present invention may further contain, in addition to the above essential components, other active components of the underwater antifouling agent within a range not to impair the scope of the present invention (other hydrophobic resins). The effect of the addition of a small amount does not show a significant difference in the effect, but the antifouling effect decreases as the amount of addition increases.)

If necessary, a desired amount of solvent can be added together with the above components. Specific examples of the solvent include benzene, toluene, xylene, methanol, ethyl acetate, methyl ethyl ketone, acetone, 1-methoxy-2.
-Propanol and the like can be used.

The method for using the underwater antifouling agent of the present invention is not particularly limited. For example, it can be applied as a paint or immersed to undersea structures such as ships, bridges, marine tanks, buoys, and power plants. Aqueducts, props for aquaculture used for aquaculture, fishing nets, fixed nets, and the like can be treated.
The material of the target fishing net is not particularly limited, for example, natural fibers such as cotton, hemp, silk, wool, polyvinyl chloride, polyvinylidene chloride, polyfluoroethylene, polyamide, polyethylene, polypropylene, polystyrene, It can be applied to fishing nets made of synthetic fibers such as polyacrylonitrile.

The amount of the underwater antifouling agent of the present invention is not particularly limited, but is about 5 to 10 g / m ² for a construction to be treated as dry weight, and about 2 to 30% by weight for a fishing net or the like. It is general that

[0025]

The underwater antifouling agent of the present invention can exert its antifouling effect continuously over a long period of time, has no problem of environmental pollution, and is highly safe for fish and shellfish and human bodies. It is effectively used as a product for the purpose of preventing the ingress of marine organisms on these bases, for example, by applying it to the surface of ships, submerged structures of underwater structures, water pipes of power plants, fish nets, etc. can do.

[0026]

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

[Synthesis Example 1] In a glass container, 137 weight of a modified silicone oil having a polyoxyethylene group, a phenyl group, and a silicon-bonded hydrogen group (ie, SiH group) in the side chain represented by the following formula A was used. Parts, MQ resin powder (0.1 mol / 100 g of terminal vinyl group, Me ₃ Si
10 parts by weight of a compound comprising _0.5 units of O and SiO ₂ units), 80 parts by weight of toluene as a solvent, 5 ppm of a platinum catalyst
And reacted at about 110 ° C. for 5 hours. Then, the solvent was removed by a rotary evaporator,
An organopolysiloxane compound in which a small amount of a hydrophobic polymer compound was bonded to a hydrophilic silicone oil was synthesized.

[Synthesis Example 2] In a glass container, 137 parts by weight of a modified silicone oil having a polyoxyethylene group, a phenyl group, and a hydrogen group in a side chain represented by the following formula A,
Q Resin powder (0.0073 mol of terminal vinyl group)
/ 100 g, a compound consisting of _0.5 units of Me ₃ SiO and SiO ₂ units), and 137 parts by weight of toluene as a solvent.
0 parts by weight and 5 ppm of a platinum catalyst were charged.
After performing the reaction for a time, the solvent was removed by a rotary evaporator to synthesize an organopolysiloxane compound in which the same amount of a hydrophobic polymer compound was bonded to hydrophilic silicone oil.

[0029]

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Example 1, Comparative Examples 1-4 As shown in Table 1, the two types of organopolysiloxane compounds obtained in the above Synthesis Examples and other compounds were blended to prepare an antifouling agent in water. Next, after immersing the fishing net in each underwater antifouling agent,
It was taken out and air-dried for 18 hours to carry out antifouling treatment.

The antifouling treatment of 400 × 200 m
m fishing net made of polyethylene was attached to a stainless steel frame and suspended at a depth of 1.5 m off the coast of Mie prefecture. The fishing net immersed in the seawater was pulled up every month, and the state of attachment of various types of marine organisms was observed. Table 1 shows the results. In addition, the evaluation numerical value of the adhesion state of the living thing in Table 1 was represented by the following criteria. 1; organisms are not attached at all. 2; organisms are partially attached in small amounts. 3: A small amount of organisms are attached as a whole. 4: The organism is quite attached as a whole. 5; The creature covers the whole surface.

The N- (fluorodichloromethylthio) phthalimide used in Table 1 has the following structure.

[0033]

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[0034]

[Table 1]

From the results shown in Table 1, the underwater antifouling agent of the present invention was
It was confirmed that the adhesion of aquatic organisms could be effectively prevented for a long period of time.

Claims (2)

[Claims] 1. The method according to claim 1, wherein 1 part by weight of the hydrophobic polymer compound is
An antifouling agent in water, comprising, as an active ingredient, an organopolysiloxane compound obtained by binding at least 2 parts by weight of a modified silicone oil having a hydrophilic functional group. 2. The underwater antifouling agent according to claim 1, wherein the hydrophobic polymer is a silicone resin.