JPH0788282B2 - Fishing net antifouling agent - Google Patents

Description

TECHNICAL FIELD The present invention relates to an antifouling agent for fishing nets, and more particularly, to a mixed aqueous solution of a water-soluble salt of polydithiocarbamic acid and a water-soluble salt of monodithiocarbamic acid, which is a metal having a valence of 2 or more. A mixed salt of polydithiocarbamic acid and monodithiocarbamic acid, which is metathesized with a salt, or, in some cases, a composition in which a single metal salt of polydithiocarbamic acid and a single metal salt of monodithiocarbamic acid are mixed with the mixed salt, and hexamethylenetetramine The present invention relates to a fishing net antifouling agent, which comprises (hereinafter referred to as HMT) as an essential antifouling material component.

2. Description of the Related Art In recent years, aquaculture of seafood has been actively carried out for the purpose of efficiently securing marine resources, but when the net used for this is immersed in the sea for a long period of time, fungi such as filamentous fungi and bacteria,
Due to the adhesion of algae, molluscs, crustaceans, shellfish, etc., the durability of the net itself is impaired or the mesh is blocked,
The movement of seawater in the net is inadequate, leading to mortality of fish due to oxygen deficiency, and also promoting the growth of bacteria, which is greatly affected by Nocardia disease, Venedeniosis caused by crustacean worms belonging to the fluke. It is known to cause damage.

A fishing net antifouling agent generally consists of two components, a coating film that coats the fishing net itself and a drug that kills adherent organisms, but the drug can kill adherent organisms for a long period of time, that is,
It is preferable that the compound has low solubility in water and has a property of being dissolved from the surface by a very small amount.

Further, it has good miscibility with the coating film, does not deteriorate the physical and chemical properties of the fishing net, and is not harmful to fish and shellfish.

Various compounds have been studied so far in order to prevent these organisms attached to fishing nets.

As typical examples thereof, copper compounds such as cuprous oxide and copper naphthenate, organic tin compounds such as tributyltin hydroxide and triphenyltin chloride, organic chlorine compounds, organic sulfur compounds and the like have been used. However, among these, there are drawbacks such as being highly toxic to humans and animals, environmental pollution, and not being able to exert a sufficient effect for a long time when used as an antifouling composition.

For example, tin compounds have a very high effect of protecting fishing nets from the adhesion of seaweed and shellfish, and have been widely used as effective antifouling components, but in recent years, their persistent properties, bioaccumulation and Animal safety and environmental pollution have begun to be a problem.

Further, for example, dithiocarbamate, which is an organic sulfur compound, is widely known as an antifouling agent component like the tin compound. For example, in JP-A-51-49227, manganese ethylenebisdithiocarbamate is used as an antifouling component,
This is mixed with a vehicle component to form a coating film component on the fishing net, preventing the attachment of organisms. In addition, similarly,
According to Japanese Patent Laid-Open No. 51-51517, a heavy metal salt of ethylenebisdithiocarbamic acid and a cellulose resin vehicle component are blended to form a coating film on a fishing net to prevent organisms from adhering.

Problems to be Solved by the Invention From various problems such as safety to human body and environmental pollution, metal dithiocarbamate is considered to be the most desirable antifouling material component, but it is satisfied with its sustainability and efficacy In many cases, it cannot be done.

Therefore, an inorganic copper compound and a heavy metal salt of alkylenebisdithiocarbamic acid are used as antifouling material components, or other antifouling components, specifically tin compounds are added thereto. Therefore, a fishing net antifouling agent having a long residual effect period and less physical and chemical deterioration of the coating film is desired.

MEANS FOR SOLVING THE PROBLEMS The present invention comprises a mixed aqueous solution of a water-soluble salt of polydithiocarbamic acid and a water-soluble salt of monodithiocarbamic acid as an essential component of a fishing net antifouling agent, which is subjected to metathesis with a metal salt having a valence of 2 or more. A mixed salt of polydithiocarbamic acid and monodithiocarbamic acid, or a composition in which the mixed salt is mixed with a single metal salt of polydithiocarbamic acid and a single metal salt of monodithiocarbamic acid, and a fishing net antifouling agent containing HMT The present invention is to provide a fishing net antifouling agent which is highly safe for human livestock and fishes, prevents adhered pollution that occurs in fishing nets, has a long residual life, and has little deterioration in fishing nets.

A mixed salt of polydithiocarbamic acid and monodithiocarbamic acid, which is obtained by subjecting a mixed aqueous solution of a water-soluble salt of polydithiocarbamic acid and a water-soluble salt of monodithiocarbamic acid used in the present invention to metathesis with a metal salt having a valency of 2 or more, or depending on the case, A composition obtained by mixing a mixed metal salt of a single metal salt of polydithiocarbamic acid and a single metal salt of monodithiocarbamic acid can be produced by a known method. For example, the mixing ratio of polydithiocarbamic acid and monodithiocarbamic acid is determined as desired. Specifically, 1: 0.1 or
1:10 (molar ratio) Preferably, it is 1: 0.5 to 1: 4, and a divalent water-soluble metal salt or zinc salt may be added to this mixture to carry out a metathesis reaction to produce the compound. As the polydithiocarbamic acid, specifically, ethylenebisdithiocarbamic acid, linear or branched propylenebisdithiocarbamic acid, linear or branched butylenebisdithiocarbamic acid, N-substituted ethylenebisdithiocarbamic acid, N,
N'-substituted ethylenebisdithiocarbamic acid, N-substituted propylenebisdithiocarbamic acid, N, N'-substituted propylenebisthiocarbamic acid, N-substituted butylbisdithiocarbamic acid, N, N'-substituted butylenebisdithiocarbamic acid, etc. Is mentioned.

Examples of monodithiocarbamic acid include methyldithiocarbamic acid, dimethyldithiocarbamic acid, ethyldithiocarbamic acid, diethyldithiocarbamic acid, propyldithiocarbamic acid, dipropyldithiocarbamic acid, butyldithiocarbamic acid and dibutyldithiocarbamic acid. The bivalent or higher valent metal salt that undergoes metathesis includes water-soluble metal salts such as zinc, manganese, iron, copper, tin, and nickel. Specifically, zinc chloride,
Examples thereof include zinc nitrate, zinc sulfate, manganese chloride, manganese sulfate, manganese sulfate, copper sulfate, copper nitrate, copper chloride, iron chloride, nickel nitrate, nickel chloride, etc., and it is also extremely effective to use two or more of them in combination. Is.

And, these can be blended in the fishing net antifouling agent in the range of 1 to 50%, preferably 1 to 20%.

Further, when HMT is added in the range of 0.01 to 20%, preferably 0.1 to 10%, a preferable effect is obtained.

The antifouling component of the present invention is a mixed salt of polydithiocarbamic acid and monodithiocarbamic acid obtained by subjecting a mixed aqueous solution of a water-soluble salt of polydithiocarbamic acid and a water-soluble salt of monodithiocarbamic acid to double decomposition with a metal salt having a valence of 2 or more, Alternatively, in some cases, the mixed salt is mixed with HMT in a slurry of a composition in which a single metal salt of polydithiocarbamic acid and a single metal salt of monodithiocarbamic acid are sufficiently mixed, and then dried and pulverized and mixed into a vehicle, that is, It may be mixed with a net dyeing ingredient.

Further, if the composition of the present invention is not sufficiently pulverized, a good fishing net antifouling agent can be obtained by kneading and stirring this component and the net dyeing component at the same time.

The fishing net antifouling agent of the present invention, as a vehicle component, animal oil, vegetable oil, natural fats and oils, acrylic resin, vinyl resin, epoxy resin, alkyd resin, and the like known,
Either may be used.

Further, known pigments in the fishing net antifouling agent of the present invention, extender pigment,
As a matter of course, auxiliary components such as a plasticizer, a solvent, an anti-caking agent and the like may be appropriately mixed.

Furthermore, it is of course possible to use known antifouling components and other pesticides in the fishing net antifouling agent of the present invention as occasion demands as a fishing net antifouling agent.

It is desirable to avoid the use of additives such as surfactants as auxiliary components of the composition of the present invention.

EXAMPLES The following examples, comparative examples, and test examples are given to illustrate the present invention. The invention is not limited to only these examples.

In the following examples, ethylenebisthiocarbamic acid was used as the polydithiocarbamic acid, dimethyldithiocarbamic acid was used as the monodithiocarbamic acid, and zinc was used as the divalent metal.

Example 1 15 parts of a composition produced from a mixing ratio of polydithiocarbamic acid and monodithiocarbamic acid of 1: 4, 1 part of HMT, 30 parts of acrylic resin and 54 parts of xylene are kneaded, mixed and stirred.

Example 2 15 parts of a composition produced from a mixing ratio of polydithiocarbamic acid and monodithiocarbamic acid of 1: 3, 1 part of HMT, 30 parts of acrylic resin and 54 parts of xylene are kneaded, mixed and stirred.

Example 3 15 parts of a composition produced from a mixing ratio of polydithiocarbamic acid and monodithiocarbamic acid of 1: 2, 1 part of HMT, 30 parts of acrylic resin and 54 parts of xylene are kneaded, mixed and stirred.

Example 4 15 parts of a composition produced from a mixing ratio of polydithiocarbamic acid and monodithiocarbamic acid of 1: 1, 1 part of HMT, 30 parts of acrylic resin and 54 parts of xylene are kneaded, mixed and stirred.

Example 5 15 parts of a composition produced from a mixing ratio of polydithiocarbamic acid and monodithiocarbamic acid of 1: 0.5, 1 part of HMT, 30 parts of acrylic resin and 54 parts of xylene are kneaded, mixed and stirred.

Example 6 15 parts of a composition produced from a mixing ratio of polydithiocarbamic acid and monodithiocarbamic acid of 1: 2, 0.5 parts of HMT, 30 parts of acrylic resin, and 54.5 parts of xylene are kneaded, mixed and stirred.

Comparative Example 1 Manganese ethylenebisdithiocarbamate (manufactured by Kumiai Chemical Industry Co., Ltd., “Mdaifer”) 10 parts, acrylic resin 35 parts, and xylene 55 parts were adjusted.

Comparative Example 2 Zinc ethylenebisdithiocarbamate (product of Kumiai Chemical Industry Co., Ltd., "Differ") 15 parts, acrylic resin 30
Part, xylene 55 parts.

Comparative Example 3 15 parts of a composition prepared from a mixing ratio of polydithiocarbamic acid and monodithiocarbamic acid of 1: 2, 30 parts of an acrylic resin and 55 parts of xylene are kneaded, mixed and stirred.

Comparative Example 4 15 parts of a composition produced from a mixing ratio of 1: 1 of polydithiocarbamic acid and monodithiocarbamic acid, 30 parts of an acrylic resin and 55 parts of xylene are kneaded, mixed and stirred.

Test example A polyethylene fishing net is cut into a size of 1.00m x 50cm,
After soaking in the antifouling agent of the present invention for 10 minutes, it was air-dried and hung in the sea within 2 m below the sea level to examine the degree of aquatic organism attachment for 3 months.

In addition, the criteria for the adhered area (state) are (1) no adherent organisms (2) adherent organisms 5% or less (3) adherent organisms 5-20% adherent (4) adherent organisms 20-50% (5) Adhered organisms 50% or more adhered

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area A01N 33:04)

Claims (1)

[Claims] 1. A fishing net antifouling agent, which comprises polydithiocarbamic acid and monodithiocarbamic acid obtained by subjecting a mixed aqueous solution of a water-soluble salt of polydithiocarbamic acid and a water-soluble salt of monodithiocarbamic acid to double decomposition with a metal salt having a valence of 2 or more. A mixed salt, or in some cases, a composition in which a single metal salt of polydithiocarbamic acid and a single metal salt of monodithiocarbamic acid are mixed with the mixed salt, and a fishing net characterized by containing hexamethylenetetramine as an essential antifouling material component Antifouling agent.