JPS6153206A - Antifouling agent - Google Patents

Abstract

PURPOSE:The titled antifouling agent that contains a polyamide resin and flat fine particles of pure metallic copper, thus showing high duration of antifouling effect for a long period of time, being usable at every place contacting water completely without anxiety of its toxicology. CONSTITUTION:A foil of pure copper of 0.025-0.035 thickness is milled and crushed to give fine particles of pure copper with a flat form which can pass through a sieve of 300 mesh. The fine particles are mixed in a polyamide solution as a binder to give the objective antifouling agent. The contents of individual components are preferably 10-20pts.wt. of pure copper, 10-25pts.wt. of a polyamide resin, 1-3pts.wt. of a plasticizer and 1-5pts.wt. of a thermoplastic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for removing algae, crustaceans, shellfish, molluscs, etc., which occur in water, from fishing nets for aquaculture, fixed nets, boat bottoms,
This invention relates to an anti-fouling agent for aquatic organisms to prevent them from adhering to and reproducing on and other marine structures. More specifically, the present invention shows no toxicity to fish, and can maintain its activity for a long period of time due to the effect of copper ions eluted from fishing nets. The present invention relates to an anti-fouling agent for aquatic organisms that has a strong synergistic effect, that is, prevents the activity of steel ions and prevents stress in cultured fish, thereby improving the promotion of fish growth without causing stress.

Fish nets for farming cattle and fixed nets, which have become popular in recent years, require immersion in seawater for a long period of time, but during this time, aquatic organisms such as algae, crustaceans, shellfish, and molluscs are It adheres to fishing nets and the ropes that form them, clogging the nets, resulting in insufficient seawater movement, resulting in the death of farmed fish due to lack of oxygen, etc., and the generation of disease-causing bacteria in the dishes, which is particularly harmful to fishing nets. In yellowtail farming, gill worms, spider worms, etc. are parasitic, and the fish have a habit of rubbing them with fishing nets to remove them, so the shells may be damaged by shellfish, especially Fujibo, etc., that are attached to fishing nets. Pseudomonas enters there, causing a purulent disease to spread, leading to mass mortality. Therefore, the fishing net must be replaced once every 1-2 months, and each time the fish are regrouped, the fish become stressed and feed poorly for 3 to 5 days, resulting in poor growth. This leads to a decline in physical strength, which weakens the resistance to various pathogenic bacteria, which in turn puts pressure on the business of fish farmers due to a deterioration in the yield of farmed fish. In addition, with fixed @ nets, the formation of fishing nets is poor due to increased resistance to ocean currents, resulting in fish escaping due to breakage of the fishing nets, and difficulty in lifting fish when replacing them due to increased weight and @.

For this reason, fishing nets are dipped in various special dyes and chemicals, dried, etc. to prevent aquatic organisms from adhering to them.

Necessary conditions for such a fishing net treatment agent include that it has low toxicity to fish, does not impair the flexibility of fishing nets, and maintains its antifouling effect over a long period of time. As fishing net treatment agents, copper compounds such as cuprous oxide and copper naphthenate, tin compounds such as tributyl pot hydroxide and triphenyltin chloride, and organic chlorine compounds such as DDTlPCP have been used, phenolic resin face, A mixture of chlorinated rubber paint or other synthetic resin paint, or a mixture of zinc ethylene bisdithiocarbamate or manganese salt and cellulose resin, etc., are used, but those that completely meet the above requirements are used. It's still unknown.

Also, most of the small fishing boats are made of FRP or resin, and 'rBTO' is used as the antifouling paint for the bottom of the boat.

In other words, it is a mixture of a tin compound such as tin oxide with another synthetic resin paint, and its toxicity has become a problem and it is hardly used at present.

As an alternative, suboxide steel, which is slightly less toxic than the tin compound mentioned above, is used mixed with other synthetic resin paints, but it has no antifouling effect on shellfish algae such as Fujibbo and Kasane Kanzaki, which tend to adhere to the bottom of ships. It will have to be repainted in about 2 to 3 months, and on top of that, there will already be a fair amount of Fujibbo, Kasane Kanzaki, etc. attached, so you will have to scrape it off with a spatula-shaped knife. , the labor costs are enormous.

Next is the problem of removing barnacles, which are most likely to adhere to pipes such as turbine cooling water pipes and drain pipes in thermal power plants and nuclear power plants, which are being frequently constructed in recent years. Fujibo originally has a tendency to prefer to attach to dark places, and its reproductive capacity is especially high among shellfish, and once it attaches, it grows to about 1.
It has grown to a thickness of about 30 to 4 Qcm per year, covering the inside of the pipe, so it has to be removed about once every six months, but once it has attached, Fujibbo has a strong adhesive force, so it is difficult to remove it. Since the concrete in that area is even peeled off, the labor costs required to remove it are enormous. Taking these into consideration, the present inventor has determined that it can be used as an aquatic organism adhesion prevention agent by coating, dipping, or both, and that it is completely non-toxic to humans and fish, and has particularly good antifouling properties. In addition to being eroded, it has a durability of more than one year, is easy to work with, and can be used in any water-contact area. As a result of repeated experiments, it was discovered that an aquatic biofouling prevention agent containing pure copper in the form of planar fine particles as an active ingredient and a polyamide resin as a binder ingredient achieves the above object, and based on this knowledge, the present invention has been made. It's arrived. That is, the aquatic biofouling inhibitor of the present invention (hereinafter abbreviated as inhibitor) is a base component commonly used in conventional fishing net treatment agents, such as a mixture of a thermoplastic resin and a plasticizer soluble in an organic solvent. is a non-toxic metal as an active ingredient,
It consists of pure copper in the form of planar fine particles produced by the manufacturing method of the present invention, which also contains a polyamide resin as a binder component, which is dissolved and dispersed in a suitable solvent. In this case, by using rosin in combination, the dispersibility and adhesion of the fishing net can be further improved. Powders of silver, copper, etc. can be used as active ingredient metals in antifouling agents, and copper powder, ie, electrolytic copper powder, is commonly used.

The present inventor previously discovered a material for cows containing pure fine copper powder mixed into a thermoplastic polyurethane resin (body thinness ÷ presently contested permit/l 13i).
Invented the J. The copper powder mixed in the resin is a commonly used fine copper powder,
The manufacturing method is an electrolysis manufacturing method.

The coarseness of copper powder produced by this manufacturing method is 3N, usually 150 to 80.
There are up to 0 mesh units, and from that, 300 to 350 mesh units of copper powder is mixed. Moreover, the mixing amount is 50% by weight. Since uniform mixing was carried out by extrusion molding, it was possible to mix uniformly into the thermoplastic polyurethane resin. However, since the polyamide resin used as the binder component in the present invention is a solution in a solvent, it has been found that it is impossible to uniformly mix common copper powder as an active ingredient. Therefore, the present inventor devoted himself to researching copper that has a shape that allows it to be mixed uniformly into a polyamide resin solution as an alternative to conventional copper powder, and as a result of repeated experiments, he succeeded in creating a planar fine particle shape. It has been found that combination with the polyamide resin of the present invention is possible due to the above-mentioned method. The method for producing pure copper in the form of planar fine particles as the active ingredient in the present invention is as follows.

For example, thickness approximately, 0.025 to 0.035 questions, width approximately,
It is manufactured with a length of about 3 to 5 Qcm and a sieve size of 5 to 10100 C or more. When this is compared with the highest conventional electrolytic copper powder, 8oO mesh copper powder, its surface area is about 40 to 50 times larger, and its volume is also about 40 to 50% larger. Therefore, even if it is mixed into the polyamide resin solution, most of it does not precipitate, allowing for uniform dispersion and mixing, making it the most suitable active ingredient for the inhibitor.

When a fishing net is treated with the inhibitor of the present invention, a smooth coating with good adhesion, which is unique to polyamide resin, can be obtained on the surface of the fishing net. In addition, since it fixes the knots of the fishing net, it is useful for preventing mesh slippage, and the elution of copper ions in the active ingredient can be sustained over a long period of time in appropriate amounts. Furthermore, the elution amount of this active ingredient is controlled to an extremely small amount, and since it is non-toxic, there is no concern about toxicity to cultured fish or useful marine resources.

The mixing ratio of each component in the present invention is, when the total is 100 parts by weight, 7 to 30 parts by weight of pure copper in the form of planar fine particles produced by the manufacturing method of the present invention, preferably 10 to 20 parts by weight, and 5 to 30 parts by weight of polyamide resin. Preferably 10 to 25 parts by weight,
0.5 to 5 parts by weight of plasticizer, preferably 1 to 3 parts by weight, 0.5 to 10 parts by weight of thermoplastic resin, preferably 1 to 5 parts by weight, and the remainder is an organic solvent. If Ronsin is used in combination, the amount should be approximately half that of the polyamide resin.

The organic solvent varies depending on the amount of solid content used, and can be increased or decreased as appropriate for the purpose of adjusting the thickness of the inhibitor coating after drying.

As the plasticizer in the present invention, conventional low-molecular plasticizers such as octyl-P oxybenzoate and benzenesulfonic acid butylamide are used. As the polyamide resin, those soluble in organic solvents such as type 6 nylon resin and type 8 nylon resin are used. Further, the thermoplastic resin is not particularly limited as long as it is a thermoplastic resin such as polyvinyl chloride, polyacrylic acid ester, vinyl acetate monomer, -poly 12-hinyl formal, etc., and is soluble in an organic solvent. Furthermore, the organic solvent may be used in combination with methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, phenol, or other solvents in order to obtain quick drying properties and compatibility of various formulations. As the rosin, gum rosin, wood rosin, tall oil rosin, etc. are used.

In order to apply the inhibitor of the present invention to a fishing net, it is preferable to immerse the fishing net in the inhibitor, sufficiently impregnate it, and then dry it. At this time, heat can be applied as desired to promote fixation of the coating. If it is difficult to soak a large fishing net, it may be carried out by spraying with an air spray gun or by applying the inhibitor to the fishing net with a brush or sponge and drying it in the sun.

Next, in order to apply the inhibitor of the present invention to the front of the bottom of a small vessel such as a fishing boat, the inhibitor may be sprayed with an air spray gun or applied with a brush and dried in the sun.

In addition, in order to apply the inhibitor of the present invention to the inside of water supply pipes such as power plants or other water-contact structures, apply the inhibitor to the water-contacted parts with a roll brush, plush, etc. and quickly dry. That's fine.

Next, the present invention will be explained in more detail with reference to Examples. All parts in each example are parts by weight.

Example 1 A polyvinyl chloride tyrene fishing net was soaked and coated with 20 parts of the active ingredient, 20 parts of Type 8 nylon resin, 3 parts of penzelsulfonic acid butylamide, and 9 parts of tall oil rosin according to the formulation of the present invention, and dried in the sun. The dried fishing net was immersed in seawater and observed. The following commonly used formulations were tested as controls:

That is, 25 parts of the active component, 25 parts of vinyl chloride, and 50 parts of thinner were uniformly dissolved and stirred, and the following observation was made in the same manner as above. Next, 20 parts of the active ingredient, 20 parts of gum rosin, 17 parts of cellulose nitrate, 5 parts of vinyl chloride resin, and 38 parts of thinner were uniformly dissolved and stirred, and the following observations were made in the same manner as above. The test was conducted for 12 months from the middle of the cattle season. The test net was about 1 m wide and about 3 m long, with a 5 cm eyepiece, and a weight was attached to the bottom of the net, which was hung with a weight exposed about 50C711 above the sea surface. The active ingredients used are as follows.

Efficacy was determined using the following stage codes based on the status of attached organisms.

As is clear from Table 1, even if pure copper in the form of planar fine particles produced by the method of the present invention is simply added to a conventional base material, its effectiveness will be reduced.

Example 2 A test was carried out with net treatment using the following composition. The test was conducted for 12 months from mid-January, and the test net had a diameter of 5 cm, a width of about 1 yn, and a length of about 3 m. Approximately 5 Q cm was exposed above the sea surface, and the remaining approximately 2.5 Q cm was suspended.

(1) As active ingredients, 20 parts of pure copper in the form of planar fine particles produced by the method of the present invention, 15 parts of type 8 nylon resin, 2 parts of benzenesulfonic acid butylamide, and 8 parts of tall oil rosin
2 parts of vinyl chloride resin, 2 parts of n-propyl alcohol, 10 parts of toluene, (2) 15 parts of pure copper in the form of planar fine particles produced by the method of the present invention as active ingredients, 15 parts of Type 8 nylon resin, benzenesulfonic acid 2 parts of butyramide,
8 parts of tall oil rosin, 3 parts of vinyl chloride, 37 parts of n-propyl alcohol, 20 parts of toluene, (3) 20 parts of pure copper in the form of planar fine particles produced by the method of the present invention as active ingredients, 15 parts of cellulose acetate, phthalate 8 parts of butyl acid, 15 parts of tall oil rosin, 2 parts of vinyl chloride vinyl acetate copolymer resin, 40 parts of thinner, (4) 15 parts of pure copper in the form of planar fine particles produced by the method of the present invention as active ingredients, 18 parts of cellulose acetate, 15 parts tall oil rosin, 7 parts diethyl phthalate, 10 parts vinyl chloride resin
(5) 20 parts of pure copper in the form of planar fine particles produced by the method of the present invention as an active ingredient, 40 parts of polyvinyl varnish, 40 parts of thinner, (6) 35 parts of thinner in the form of planar particles produced by the method of the present invention as the active ingredient. 20 parts of pure copper, 50 parts of chlorinated rubber paint, 30 parts of thinner, (7) 20 parts of pure copper in the form of planar fine particles produced by the method of the present invention as active ingredients, 30 parts of acrylic ester resin, 50 parts of thinner, (8) Active ingredients. Ingredients: 15 parts pure copper in the form of planar fine particles produced by the method of the present invention, 40 parts of phenolic resin face, 45 parts of solvent naphtha; (9) 20 parts of pure copper in the form of planar particles produced by the method of the present invention as active ingredients, vinyl acetic acid chloride Vinyl copolymer resin 30
part, 50 parts of solvent naphtha, (1) to (2) are the compositions of the present invention, and (3) to (9) only the active ingredients are pure copper in the form of planar fine particles of the present invention, and the binder component is the conventionally used pure copper. or commonly used formulations. The results are shown in Table-2.

Table 2 Example 3 According to the formulation of the present invention, 20 parts of the active ingredient, 20 parts of Type 8 nylon resin, 10 parts of gum rosin, 2 parts of vinyl chloride resin, 30 parts of ethyl alcohol, and 18 parts of toluene were uniformly mixed, dissolved, and stirred. This was applied to a Fnr tree board with a thickness of about 10M, a length of about 1m, and a width of about 5Qcm, and the board was immersed in seawater and observed. As a control, the following commonly used formulations were tested.

That is, 25 parts of the active ingredient, 25 parts of vinyl chloride, and 50 parts of thinner were uniformly mixed and dissolved, stirred, and observed in the same manner as described below. The test started in mid-January, and one part was immersed in seawater for a month.

The test FRP and resin plates were suspended below the sea surface at l-2772. The active ingredients used are as follows.

Efficacy was determined using the following stage codes based on the occurrence of attached organisms.

If added to a drug, the effect will be reduced.

Example 4 The following composition was applied to a test FRP resin plate with a thickness of about 10 mm, a breakage of 1 m, and a width of about 5 Qcm1, and was tested. The test will begin in mid-January and will be conducted for 15 months at 1-2 meters below sea level.
It was hung on.

(1) The active ingredients include 25 parts of pure copper in the form of planar fine particles produced by the method of the present invention, 20 parts of type 8 nylon resin, 2 parts of benzenesulfonic acid butylamide, and 10 parts of tall oil rosin.
parts, vinyl chloride resin 3 parts, n-propyl alcohol 30 parts
(2) Active ingredients include 18 parts of pure copper as planar fine particles produced by the manufacturing method of the present invention, 20 parts of type 8 nylon resin, 2 parts of benzenesulfonic acid butylamide, 10 parts of tall oil rosin,
2 parts vinyl chloride fat control, 30 parts n-propyl alcohol,
18 parts of toluene, (3) The active ingredient is a flat body produced by the method of the present invention! To! 15 parts of pure copper, 20 parts of type 8 nylon resin, 2 parts of benzenesulfonic acid butylamide, 1 part of tall oil rosin
0 parts, vinyl chloride resin 2 parts, n-propyl alcohol 3 parts
1 L) - 2 parts of toluene, (4) Active ingredients include 25 parts of pure copper in the form of planar fine particles produced by the manufacturing method of the present invention, 30 parts of vinyl chloride resin, and 4 parts of thinner.
(5) The active ingredients include 20 parts of pure copper in the form of planar fine particles produced by the production method of the present invention, 30 parts of chlorinated rubber paint, 10 parts of tall oil rosin, and 40 parts of thinner. (7) The active ingredients include the following: 20 parts of pure i in the form of planar fine particles according to the manufacturing method, 40 parts of vinyl chloride vinyl acetate copolymer resin paint, 40 parts of thinner
(8) The active ingredients are 20 parts of pure copper in the form of planar fine particles produced by the manufacturing method of the present invention, 40 parts of alcohol-soluble phenolic resin paint, and 40 parts of thinner. ) to (8), the active ingredient is a pure network in the form of planar fine particles produced by the production method of the present invention, and the binder component is a conventionally used one or a commonly used formulation.

Table 4 Efficacy was determined in the same manner as in Example 1 based on the occurrence of attached organisms.

Judging from Table 4 above, the aquatic biofouling inhibitor of the present invention is
It has long-term antifouling properties, can be used in any water-contact area, and most importantly, there is no need to worry about toxicity, providing an innovative aquatic biofouling prevention agent. It is something.

Claims (1)

[Claims] An underwater biofouling prevention agent characterized by containing a combination of polyamide resin and pure copper in the form of planar fine particles as a main component, and a method for producing the pure copper in the form of planar fine particles.