JPH11193203A - Aqueous antifouling agent for fishing net - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a safe aqueous antifouling agent for fishing nets excellent in antifouling effect for fishing nets and extremely slight in environmental pollution by including a specific active ingredient, a spreading resin, a specific elution controller, a surfactant and water. SOLUTION: This antifouling agent for fishing nets comprises (A) about 8-20 wt.% active ingredient comprising dithiocarbamic acid compound of the formula (M is Zn or Cu), (B) about 5-30 wt.% spreading resin which is a mixed resin, preferably containing an acrylic resin and a polyisobutylene at (1:1) to (1:8) mixed ratio, (C) about 0.5-1 wt.% elution controller comprising a cellulose derivative (e.g. hydroxypropyl cellulose), (D) about 1-5 wt.% surfactant as a disperse stabilizer or a penetrating agent and (E) water as a solvent. When the acrylic resin and the polyisobutylene are compounded with the antifouling agent for fishing nets, it is preferable that these polymers are previously prepared in emulsion form by adding an emulsifier to these polymers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a practical water-based fishing net which can prevent functional damage due to the attachment of organisms to a fishing net immersed in water for a long period of time, and which is safe in handling and has very little environmental pollution. It relates to an antifouling agent.

[0002]

2. Description of the Related Art A variety of organisms, such as plants and animals, adhere to aquaculture and stationary fishing nets installed in water for a long time. Adhesion of these organisms can lead to mass destruction of farmed fish due to oxygen deficiency due to mesh occlusion, and also cause loss of fishing nets due to increased flow resistance. In addition, since the weight of the net increases due to the adhesion of organisms, re-netting, net-lifting, and net cleaning require more labor. Among them, bryozoans, barnacles and hydro insects are pests that grow quickly and cause problems in a short period of time, and effective fishing net antifouling agents are expected.

As a countermeasure against this, dithiocarbamic acid compounds have long been known to be effective and have been used in practice. In recent years, JP-A-6-157219 discloses a dithiocarbamic acid compound having an average particle size of 2 μm or less as an active ingredient.
A non-aqueous underwater antifouling agent using xylene or the like as a solvent has been proposed. However, existing antifouling agents containing this antifouling agent include:
As a solvent, a flammable volatile organic solvent (hereinafter, also referred to as an organic solvent) corresponding to a dangerous substance under the Fire Service Law is used.
Such organic solvents may cause inhalation poisoning by workers due to inadequate handling in the antifouling treatment of fishing nets,
There is a risk of fire explosion and fire. In addition, during drying after application, these organic solvents usually contained in the preparation in an amount of 40 to 70% are released into the atmosphere, which causes environmental pollution.

In order to solve such a problem, an aqueous emulsion paint type fishing net antifouling agent using water as a solvent, which is widely used as a land-based exterior paint, has been considered. In the gazette, an aqueous antifouling agent in which an N-alkylpolyamine compound is used as an active ingredient and a synthetic resin is emulsified by using the compound as an emulsifier has begun to be proposed. Older is JP-A-51-14936
A water-based antifouling paint used for ship bottoms is disclosed in Japanese Patent Application Publication No. H07-187, but an aqueous fishing net antifouling agent containing a compound having excellent antifouling effect and low water solubility as an active ingredient has not yet been put to practical use. .

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous fishing net antifouling agent which can be used in place of a non-aqueous fishing net antifouling agent using an organic solvent as a solvent. That is, to provide an aqueous fishing net antifouling agent that is safe in handling and does not cause environmental pollution because it does not contain a large amount of organic solvent as a solvent, and has the same or better effect than a nonaqueous fishing net antifouling agent. With the goal.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on an aqueous fishing net antifouling agent. As a result, a dithiocarbamic acid compound is used as an active ingredient for inhibiting the attachment of organisms, and the active ingredient is retained on the net. Acrylic resin and polyisobutylene are preferably used as the spreading resin to be gradually eluted in water, and a cellulose derivative is used as an elution modifier for controlling the elution rate of the active ingredient and the elution rate of the spreading resin at a constant level. In addition, the spreading resin is evenly dispersed in the fishing net antifouling agent, and these are penetrated to the inside of the net during the antifouling treatment, and a surfactant is used as a dispersion stabilizer and a penetrating agent that improves drainage when pulled up and dried. By blending and stabilizing the dispersion of the components, it is possible to obtain the same permeability to the net as that of the existing non-aqueous fishing net antifouling agent. Since the preparative spreading resin is efficiently eluted, onsets viewed knowledge that the antifouling effect can be maintained for a long time, and have completed the present invention. That is, the present invention includes the following inventions.

(1) General formula (I)

Embedded image (Wherein M represents Zn or Cu) a fishing net antifouling agent containing a dithiocarbamic acid compound represented by the following formula as an active ingredient, a spreading resin, an elution modifier, a surfactant, and water as a solvent. A fishing net antifouling agent, wherein a cellulose derivative is used as an elution modifier.

(2) The fishing net antifouling agent according to (1), wherein the spreading resin is a mixed resin of an acrylic resin and polyisobutylene. (3) The mixing ratio of acrylic resin and polyisobutylene is 1:
The fishing net antifouling agent according to (3), which is 1-1: 8. (4) The fishing net antifouling agent according to (1) to (3), wherein the cellulose derivative is hydroxypropyl methylcellulose. (5) The fishing net antifouling agent according to (1) to (4), which is in the form of an emulsion. (6) The fishing net antifouling agent according to (1) to (5), wherein the dithiocarbamic acid compound is used in an amount of 8 to 20% by weight based on the total weight of the fishing net antifouling agent.

(7) The fishing net antifouling agent according to (1) to (6), wherein the spreading resin is used in an amount of 5 to 30% by weight based on the total weight of the fishing net antifouling agent. (8) The fishing net antifouling agent according to (1) to (7), wherein the cellulose derivative is used in an amount of 0.05 to 1% by weight based on the total weight of the fishing net antifouling agent. (9) 1 to 5 surfactants based on the total weight of the fishing net antifouling agent
The fishing net antifouling agent according to (1) to (8), which is used by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the aqueous fishing net antifouling agent of the present invention, a dithiocarbamic acid compound is contained in an amount of about 8% based on the total weight of the fishing net antifouling agent, depending on the appearance of organisms and the degree of fouling depending on the sea area.
It is used in the range of -20% by weight, with about 10-16% by weight being particularly preferred. If the amount is less than about 8% by weight, the long-term antifouling effect becomes insignificant. If the amount exceeds about 20% by weight, the permeability of the netting material decreases due to an increase in the viscosity of the antifouling agent. Tend to weaken.

These dithiocarbamic acid compounds are usually used alone. However, since the spectrum is expanded by the difference of the attached organism species appearing in water, 2,4,5,6 -Tetrachloroisophthalonitrile, 2-methylthio-4-t-butylamino-
6-cyclopropylamino-s-triazine, N, N-
Dimethyldichlorophenylurea, tetramethylthiuram disulfide, 2,3,5,6-tetrachloro-4-
(Methylsulfonyl) pyridine, N- (fluorodichloromethylthio) phthalimide, 2-pyridinethiol-
1-oxide zinc salt, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, 4,5-dichloro-2-n-octyl-3- (2
One or more selected from H) -isothiazolones may be blended in a range of 0.05 to 0.5 times the weight of the dithiocarbamic acid compound. However, it is preferable that the total weight of the fishing net antifouling agent and the dithiocarbamic acid compound is about 20% by weight or less.

It is well known that the smaller the particle size of these active ingredients, the better the permeability into the interior of the netting and the higher the efficacy. Therefore, it is desirable to grind beforehand when preparing the fishing net antifouling agent, and then mix it with other components, and it is preferable that the particle size is about 10 μm or less. Acrylic resin used as the spreading resin of the aqueous fishing net antifouling agent of the present invention is acrylic acid, methacrylic acid or a copolymer of esters thereof or a light metal salt thereof (Li, Na, K, Ca, Mg, Al),
Mainly ammonium salts or mixtures thereof,
Maleic acid, fumaric acid, itaconic acid and other acid components, styrene, α-methylstyrene, acrylonitrile and other hard components and butyl acrylate, 2-ethylhexyl acrylate and other soft components are appropriately copolymerized into synthetic fibers. The composition is not particularly limited as long as it is a composition that can provide adhesiveness and high water resistance. However, a composition having an average molecular weight of tens of thousands to hundreds of thousands and having a glass transition temperature of room temperature or lower is desirable.

The polyisobutylene also used as the spreading resin may be a chain hydrocarbon mainly composed of isobutylene, and may be a copolymer obtained by partially copolymerizing normal butylene.
Any one having an average molecular weight of about 100 to 60,000 or a mixture thereof can be arbitrarily selected depending on the type of net or sea area. The mixing ratio of these acrylic resin and polyisobutylene varies depending on the amount of the dithiocarbamic acid compound as the active ingredient or the type of fishing net used,
Usually, the weight ratio is about 1: 1 to 1: 8, and preferably about 1: 1 to 1: 5. If the mixing ratio of the acrylic resin is higher than this range, the coating film tends to be strong and the flexibility of the net tends to decrease, and it is also difficult to stabilize the dissolution rate with the dissolution controlling agent. Conversely, if the blending ratio of polyisobutylene exceeds this range, the net tends to be sticky after the treatment and drying. The total weight of the acrylic resin and polyisobutylene is about 5 to 30 with respect to the total weight of the fishing net antifouling agent.
%, Preferably about 8 to 25% by weight. When the total amount of the acrylic resin and polyisobutylene is less than about 5% by weight based on the total weight of the fishing net antifouling agent, the ability to retain the active ingredient in water is not remarkable. There is a tendency for the permeability of the antifouling agent to decrease due to the increase in viscosity.

When the acrylic resin and polyisobutylene are blended with the antifouling agent for fishing nets, it is desirable to add an emulsifier by the following method to prepare an emulsion in advance. That is, the acrylic resin emulsion is about 0.2 to 12% by weight, preferably about 1 to
It is a usual emulsion resin obtained by dropping a mixed monomer into an aqueous solution containing 4.5% by weight of an emulsifier and about 0.2 to 4.5% by weight of an initiator and performing copolymerization. Any of redox polymerization can be suitably used. On the other hand, a polyisobutylene emulsion can be obtained by adding water while kneading a mixture with an appropriate amount of an emulsifier. As these emulsifiers, a nonionic surfactant, an anionic surfactant, or a mixture thereof can be used. However, from the viewpoint of emphasizing the stability of the emulsion system, the anionic surfactant alone or the anionic surfactant can be used. It is preferable to use a system obtained by mixing a nonionic surfactant in an amount of not more than half with the main component.

The cellulose derivative to be added as the dissolution controlling agent is, for example, a water-soluble cellulose derivative such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and has an average molecular weight of 50,000 to 1
A thing of 00,000 is preferred. Cellulose derivatives are
It is arbitrarily selected to fine-tune the elution amount of the fishing net antifouling agent due to differences in the environment of the sea area used such as water temperature and flow velocity,
They may be used alone or in combination of two or more. Preferably, hydroxypropyl methylcellulose and carboxymethylcellulose are used.

These cellulose derivatives vary depending on the amount of the dithiocarbamic acid compound or the type of fishing net used, but are usually about 0.05 to the total weight of the fishing net antifouling agent.
-1% by weight. If the compounding ratio is largely outside the above range, the elution of the active ingredient dithiocarbamic acid compound and the spreading resin becomes slow and the effect is not remarkable, and conversely, the elution of the dithiocarbamic acid compound and the spreading resin is too fast and expected effect. The period may be shorter.

Examples of the surfactant used as the dispersion stabilizer or the penetrant include the following, but are not limited to these examples. For example, alkylaryl sulfonates, sulfonates of dibasic fatty acid esters, higher alcohol sulfates,
Higher alcohol phosphate salts, anionic surfactants such as aliphatic amide sulfonates, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene sorbitan alkyl esters, or A mixture of two or more of these surfactants can be used.

These surfactants vary depending on the amount of the dithiocarbamic acid compound or the type of fishing net to be used, but are usually used alone or in combination of two or more to provide about 1 to 5% by weight based on the total weight of the fishing net antifouling agent. %. If the amount is significantly outside the range, the dispersibility is reduced, and adhesion spots such as an active ingredient of a dithiocarbamic acid compound are generated.
The elution of the dithiocarbamic acid compound and the spreading resin tends to be too fast to shorten the expected effect period, and the antifouling effect tends to be insignificant.

The fishing net to which the water-based fishing net antifouling agent of the present invention is applied has a wide variety of materials, shapes, and new and old state changes. For example, the material is polyethylene, polyester,
There are types such as polyvinylidene chloride and their mixed twist. Shapes include knots, no knots, monofilaments, and multifilaments. Speaking of the change in state between old and new, there is a difference that the surface of the new net is smooth, and that the old net has a more prominent surface. The number of twisted fibers differs depending on the size of the mesh and the thickness of the mesh. Therefore, the specific gravity, the area, and the like of each net are different, and the way of receiving flowing water resistance in water and the movement of the net are various. These differences are factors that change the dissolution property of the antifouling agent,
The optimum conditions are adjusted by the compounding ratio and compounding amount of the spreading resin and the dissolution modifier, but in some cases, the following rosin is used to provide the fishing net antifouling agent of the present invention to each object as the optimum. , Wax and the like can be blended in the form of an emulsion as an adhesion regulator to adjust the adhesion of the fishing net antifouling agent to the net.

The rosins mentioned here are natural rosins, synthetic rosins or modified rosins, and the waxes are aliphatic hydrocarbons, higher fatty acids, fatty acid amides, fatty acid esters, polyethylenes, polypropylenes and the like. Wax or the like, but is not limited thereto. Further, water is used as a solvent in the aqueous fishing net antifouling agent of the present invention. However, in order to enhance drying and permeability, depending on the antifouling object, about 0.05 to 5% by weight based on the total weight of the fishing net antifouling agent. May be blended.

Further, although the fishing net antifouling agent is usually colored with dyes and pigments, the fishing net antifouling agent of the present invention can be colored with an appropriate dye and pigment. The fishing net antifouling agent of the present invention can be prepared by mixing and stirring the above components. The fishing net antifouling agent of the present invention thus prepared can be applied by appropriately using a normal coating method such as immersion, brush coating, spraying, etc., depending on the fishing net to be used, and at normal temperature or under heating. And dried on a fishing net.

[0022]

EXAMPLES Hereinafter, the aqueous fishing net antifouling agent of the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Example 1 A fishing net antifouling agent was prepared by mixing and stirring each component according to the formulation examples and comparative formulation examples shown in Table 1. The resulting fishing net antifouling agent was immersed for 15 seconds in 24 sections of 24 pieces of polyethylene 400D, cut into 6 pieces x 6 pieces x 6 pieces, and dried at room temperature for 7 days. According to the following formula, the required weight of the fishing net antifouling agent required for the antifouling treatment of the fishing net, that is, the ratio of the use of the fishing net antifouling agent to the net weight (consumption rate), the attached weight of the active ingredient in the fishing net antifouling agent to the net weight The ratio (active ingredient adhesion rate) was determined.

In Table 1, the acrylic resin emulsion and the acrylic resin xylene solution were respectively Marposol F-1 manufactured by Matsumoto Yushi Seiyaku Co., Ltd. (average molecular weight 50,000).
１００100,000), Marposol N250 (average molecular weight 50,000-60,000), Mitsubishi Rayon (
LR-155 (average molecular weight 60,000-80,
000). The i, n-butylene copolymer emulsion and the i, n-butylene copolymer were manufactured by Nippon Petrochemical Co., Ltd., HE-175 (average molecular weight: about 900) and HE, respectively.
-1975 (average molecular weight about 2,300), HV-10
0 (average molecular weight about 900). Surfactants and, respectively, Himal CS- manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.
40L, Sylvan T-80, and Hymar 585. Hydroxypropyl methylcellulose used had an average molecular weight of about 86,000.

[0024]

(Equation 1)

[0025]

(Equation 2)

[0026]

(Equation 3)

[0027]

[Table 1]

Example 2 In the same manner as in Example 1, 24 sections of polyethylene 400D, which is cut to length × width: 10 mesh × 10 mesh, 10 section fishing net pieces were prepared according to the formulation examples and comparative formulation examples shown in Table 1. It was immersed in a fishing net antifouling agent for 15 seconds and dried at room temperature for 7 days. These are 1.5 times below sea level in the culture area off the coast of Kuchino off Numazu City, Shizuoka Prefecture.
m for a period of 5 months from June. The state of biofouling was observed every month. Table 2 shows the results.

[0029]

[Table 2]

Example 3 A fishing net treated with each fishing net antifouling agent in Example 1 was suspended in two 60 L water tanks containing artificial seawater, and the seawater was gradually dissolved at a water temperature of 23 ° C. and a flow rate of about 1.5 knots. The stirring was performed while changing the temperature. At 1, 2, and 3 months, a portion of the fishing net piece was cut out and the residual ratio of the active ingredient was examined. Table 3 shows the results.

[0031]

[Table 3]

As is clear from Tables 2 and 3, it was found that the antifouling agent for fishing nets of the present invention has a uniform active ingredient dissolution property and a long lasting effect. However, if the amount of each component is out of the preferred range, the active ingredient adheres much to the surface of the netting, but the permeability decreases (Comparative Formulation Examples 1 and 4), or the water solubility of the fishing net antifouling agent component Is too high (Comparative Prescription Examples 3 and 5), and the initial dissolution of the active ingredient is large, so that it is difficult to obtain the persistence of the dissolution. Also, the coating film becomes strong (Comparative Prescription Example 2), and the active ingredient is hardly eluted. Problems tend to occur, and the effect tends to be less remarkable. Comparative Formulation Example 6 is an organic solvent type fishing net antifouling agent in which the amount of the spreading resin was the same as the present fishing net antifouling agent. Therefore, it was found that the water-based fishing net antifouling agent of the present invention exhibited the same or better effect than the non-aqueous fishing net antifouling agent.

Example 4 In the same manner as in Example 1, length x width: 8 meshes x 8 meshes of 24 sections of polyethylene 400D 24 knots were used.
Was immersed in a fishing net antifouling agent prepared according to Formulation Examples 5 and 6 and Comparative Formulation Example 7 for 15 seconds, and dried at room temperature for 7 days. Also, 90 × 90 mm fishing net pieces made of 90 pieces of polyester 250D cut into 3 mesh × 3 mesh in 3 mesh × 3 mesh were similarly applied to fishing net antifouling agents prepared according to Formulation Examples 7 and 8 and Comparative Formulation Example 8 shown in Table 5 for 15 seconds. It was immersed and dried at room temperature for 7 days. These are set off the coast of Hayakawa, Odawara City, Kanagawa Prefecture.
m for a period of 5 months from June. The state of biofouling was observed every month according to the criteria of Example 2. Table 5 shows the results. In Table 4, the same acrylic resin emulsion and acrylic resin xylene solution as in Table 1 were used, and the same i, n-butylene copolymer emulsion as in Table 1 was used. Japan Petrochemical
HV-1900 manufactured by K.K. (average molecular weight: about 2,300) was used. The same surfactant as in Table 1 was used.

[0034]

[Table 4]

[0035]

[Table 5]

According to Tables 4 and 5, in the fixed sea area, a polyester net is often used in addition to the polyethylene net.
It was found that the fishing net antifouling agent of the present invention exhibited a good effect even when the sea area and the type of net were changed.

[0037]

As described above, the fishing net antifouling agent of the present invention, which contains a dithiocarbamic acid compound, an acrylic resin, a polyisobutylene, a cellulose derivative, a dispersant and a penetrant in a certain range, prevents the adhesion of pests for a long period of time. In addition, since no organic solvent is used, handling is safe and air pollution is extremely small.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 55/02 A01N 55/02 B (72) Inventor Yoshinori Sano 328 Shiotanihamano, Fukuda-cho, Fukuda-cho, Iwata-gun, Shizuoka Pref. (72) Inventor Yoshio Sasaki 2-3-1 Shibukawa-cho, Yao-shi, Osaka Matsumoto Yushi Pharmaceutical Co., Ltd.

Claims (9)

[Claims] 1. A compound of the general formula (I) (Wherein M represents Zn or Cu) a fishing net antifouling agent containing a dithiocarbamic acid compound represented by the following formula as an active ingredient, a spreading resin, an elution modifier, a surfactant, and water as a solvent. A fishing net antifouling agent, wherein a cellulose derivative is used as an elution modifier. 2. The fishing net antifouling agent according to claim 1, wherein the spreading resin is a mixed resin of an acrylic resin and polyisobutylene. 3. The fishing net antifouling agent according to claim 2, wherein the mixing ratio of the acrylic resin and the polyisobutylene is from 1: 1 to 1: 8. 4. The fishing net antifouling agent according to claim 1, wherein the cellulose derivative is hydroxypropyl methylcellulose. 5. The fishing net antifouling agent according to claim 1, which is in the form of an emulsion. 6. The method according to claim 1, wherein the dithiocarbamic acid compound is used in an amount of 8 to 20% by weight based on the total weight of the fishing net antifouling agent.
The antifouling agent for fishing nets according to any one of the above. 7. The fishing net antifouling agent according to claim 1, wherein the spreading resin is used in an amount of 5 to 30% by weight based on the total weight of the fishing net antifouling agent. 8. The fishing net antifouling agent according to claim 1, wherein the cellulose derivative is used in an amount of 0.05 to 1% by weight based on the total weight of the fishing net antifouling agent. 9. The fishing net antifouling agent according to claim 1, wherein a surfactant is used in an amount of 1 to 5% by weight based on the total weight of the fishing net antifouling agent.