JPS6268863A - Antifouling agent for fishing nets - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel antifouling agent for fishing nets. ◎Aquatic materials such as aquaculture nets and treasure fishing nets for marine fish or fishing ropes are suitable for use in fishing nets such as fretsubo, serpura, oysters, etc. Green algae, diatoms, brown algae represented by marine animals, blue laver, and sea lettuce,
Marine plants such as red algae attach to the fishing nets, clogging the fishing nets and causing poor drainage, which has caused a variety of damage, including mass death of fish and outbreaks of disease.

Conventionally, measures to prevent the adhesion of these marine contaminants have been to impregnate nets or ropes with paints containing biologically active compounds such as suboxide steel and organotin compounds as antifouling ingredients. At present, membrane components are relied solely on highly toxic components to prevent adhesion. This method utilizes the phenomenon that the concentration of toxic components near the logical membrane exceeds the lethal concentration of living organisms, thereby preventing their attachment and inhabitation.

In such known methods, the most commonly used antifouling component is a tributyltin compound; bistributyl/L'fi oxide (TBTO) is used in combination with a resin binder, or tributyltin acrylate or methacrylate is used in combination with a resin binder. Polymers or copolymers are often used by processing them into nets, but the content of metallic tin in this case is 2.
If the content is less than this, it is difficult to guarantee the antifouling effect of fishing nets for more than eight months. Therefore, the antifouling effect can be enhanced and the effect can be maintained for a long time. In order to do this, it is necessary to increase the content of organotin compounds as metal complexes in the antifouling agent, but if such antifouling ingredients are used in excessive amounts, seawater contamination will occur rapidly due to the elution of toxic components. As a result, the present inventors have determined that the content of biologically active antifouling components can be increased without reducing the antifouling effect. Developing an antifouling agent with a small amount It was discovered that an antifouling effect equal to or greater than that of a staining agent can be obtained, leading to the present invention. In other words, the present invention contains a super absorbent resin, an organic tin compound, an organic binder, and an organic solvent. Provides an antifouling agent for fishing nets characterized by This is a book that prevents the adhesion of marine organisms over an invasive period through interactions between Any material may be used as long as it swells and retains water but is not substantially dissolved in water. However, the amount of water absorbed is less than 20 times its own weight, and there is a large amount of super absorbent resin added to make the paint film surface antifouling in water. Preferred shape and particle size are not particularly limited, but from the viewpoint of processability as an antifouling agent and stability of slurry, it is desirable that the particle size be as fine as possible, with an average particle size of 100 μm. Preferably 60μ or less
The following are good.

Examples of such superabsorbent resins include saponified starch-acrylic nitrile graft polymers, starch-acrylic acid polymers,
saponified product of vinyl acetate-acrylic acid ester copolymer,
Saponified products of vinyl acetate-α, β-unsaturated dicarboxylic acid ester copolymers, crosslinked products of modified isobutylene-maleic anhydride copolymers, acrylic acid polymers having a crosslinked structure, polyethylene oxide V-dos-based modified products, Known super absorbent resins include crosslinked polyvinyl alcohol, saponified polyacrylonitrile, crosslinked polyacrylamide, acrylic acid-acrylic acid ester copolymers, and mixtures thereof. Among them, super absorbent resins such as polymer electrolytes containing carboxylic acid salts having a crosslinked structure have a water absorption capacity of 4.
It is desirable to use organic tin compounds because they are highly effective and have excellent antifouling effects. The organic tin compounds used in the present invention are generally used as bactericidal agents, antifungal agents, and antifouling agents. Tributyltin compounds such as bistributyltin oxide, tributyltin chloride, tributyltin chloride, tributyltin (meth)acrylate polymers or copolymers; Examples include physiologically active compounds such as triphenyltin compounds such as phenyltin (meth)acrylate polymers or copolymers. Among these organic tin compounds, triglytin (meth)acrylate polymers or copolymers The polymer, triphenyltin (meth)acrylate or copolymer has a polymer structure in which tin is bonded within the molecule and also has properties as a binder.The organic binder used in the present invention is It is not particularly involved in the antifouling effect, but instead serves as a binder that stably fixes the superabsorbent resin and organic tin compound to the surface of the fishing net for a long period of time. Examples of such organic binders include chlorosulfonated polyethylene, Rubber binders such as chloroprene rubber, polybutadiene, chlorinated butyl rubber, chlorinated polyethylene, nitrile rubber, polyurethane rubber, and chlorinated rubber; and water-insoluble synthesis of acrylic resins, polyurethane resins, polyester resins, vinyl chloride resins, and vinyl acetate resins. These organic binders may be used alone or in combination of two or more, but if a rubber binder such as chlorinated polyethylene or chloroprene rubber is used in combination with a resin binder, The coating film is highly flexible,
The coating performance is often improved compared to resin-based resins alone, such as superior abrasion resistance.In addition, the organic solvent adjusts the viscosity and concentration that are practically suitable when treating fishing nets with antifouling agents. A melting method that simultaneously dissolves the organic compound and the organic binder is selected. There are no particular restrictions on the solvent, aromatic or aliphatic, etc., and the process of impregnating the net is In consideration of the properties and dry nature of the eel, those having a boiling point at normal pressure in the range of 50 to 150°C are preferable.・Especially aromatic systems such as benzene, F-ene, and xylene, acetone, methyl ethyl ketone,
Aliphatic solvents such as methyl isobutyl ketone and acetic acid ester/I/ are advantageous from the viewpoint of stability, and in some cases two or more solvents may be used in combination to improve solubility. In the antifouling agent for fishing nets of the present invention, the content of the above-mentioned components in the antifouling agent, practical work, properties, suitable coverage amount for fishing nets, and sustainability of the antifouling effect in water, etc. The content of the super absorbent resin is generally selected from the following range. If it is less than 2%, the effect of preventing the adhesion of contaminant organisms and its sustainability will be poor;
If the content exceeds 0%, the mechanical stability and workability of the antifouling agent slurry may be affected.
．． If it is less than 0.2%, the effect will be that of the superabsorbent resin alone, and a sufficient synergistic effect will not be obtained.
*If the antifouling effect itself is exceeded, there will be no adverse effect on the antifouling effect itself, but the product will have a high concentration similar to conventional products and may cause environmental pollution. In particular, the antifouling agent of the present invention However, even with a low concentration of organic content (less than 2%) in the metal part, which was previously thought not to be sufficiently effective, it can be used for a long period of time due to the Izumi effect with the super absorbent resin. Considering that the antifouling effect can be obtained, there is no need for the content of the metal part to exceed 2%.◎ The content of #II type binder is usually 6 to 60%, but less than 5%. If it exceeds 50%, the holding power as a binder is poor, while if it exceeds 50%, it becomes highly viscous and has poor processability into fishing nets. Basically, the antifouling agent for fishing nets of the present invention has It consists of the above-mentioned super absorbent resin, organic tin compound, organic binder, and organic solvent, but if necessary, it may also contain acidity/l/l/um, carbon black, dye, pigment, dispersant, thickener, Additives such as stabilizers may be added as subcomponents. The antifouling agent for fishing nets of the present invention is generally produced by dissolving it in organic matter. Uniform dispersion of the resin is important, and any order of addition and any dispersion method may be used as long as uniform dispersion is achieved.

The antifouling agent for fishing nets of the present invention produced in this manner can be processed by general methods such as shaving coating, spray coating, and low μ coating. However, when processing aquaculture nets and fixed nets, Immerse the aquaculture net or fixed net in the antifouling agent slurry and apply the antifouling agent.
A common method is to impregnate J& fiber and allow it to dry naturally in the atmosphere.

Fishing nets processed with the antifouling agent for fishing nets of the present invention have a very small effect on environmental pollution of seawater and fishes, but can stably obtain the effect of preventing the attachment of marine pollutants over a long period of time. .

Next, the present invention will be explained with reference to examples, but the present invention is not limited to these examples only. Examples 1 to 7. Comparative Examples 1 to 6 While stirring, a predetermined amount of an organic tin compound and an organic binder were dissolved in an organic solvent, a predetermined amount of a super absorbent resin was added thereto, and the mixture was sufficiently stirred to disperse. The antifouling agents for fishing nets shown in the table were prepared.

For comparison, antifouling agents were similarly prepared that did not contain some of the above components.

Table 1 shows these blending ratios.

A polyethylene fishing net was immersed in each of the obtained antifouling agents, and the impregnated net was air-dried overnight at room temperature.
50 CHI) was fixed and immersed approximately 1m below the sea surface in the Yokosuka-type Nagai fishing port, and the adhesion status of marine contaminants was investigated under the same conditions.The results of these seawater immersion tests are shown in Table 2. The evaluation of the 0 test shown was performed on an 8-level scale as shown below.

A: Adhesion of marine contaminants is not observed. OB: Slight adhesion of marine contaminants is observed, but it can be used practically.

C: The adhesion of marine contaminants is so significant that it cannot be used as a fishing net. In Table 2, Comparative Example δ is the result for a totally untreated fishing net. )

Claims (5)

[Claims] (1) An antifouling agent for fishing nets containing a superabsorbent resin, an organic tin compound, an organic binder, and an organic solvent. (2) The antifouling agent for fishing nets according to claim 1, wherein the superabsorbent resin is a polymer electrolyte containing a carboxylate in its molecule. (3) Antifouling for fishing nets according to claim 2, wherein the super absorbent resin is a saponified product of vinyl acetate-acrylic ester copolymer or a crosslinked product of a modified isobutylene-maleic anhydride copolymer. agent. (4) The antifouling agent for fishing nets according to claim 1, wherein the organotin compound is a tributyltin compound or a triphenyltin compound. (5) The superabsorbent resin content is 2 to 80% by weight, the organic tin compound content is 0.2 to 2% by weight as metal tin, the organic binder content is 6 to 50% by weight, and the remainder is an organic solvent. An antifouling agent for fishing nets according to claim 1.