JPH0788283B2 - Fishing net antifouling agent - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a fishing net antifouling agent, and more specifically, a lower alkylenebisthiocarbamic acid heavy metal salt and hexamethylenetetramine (hereinafter referred to as HMT) are essential preventive agents. The present invention relates to a fishing net antifouling agent that is contained as a soil component.

(Prior Art) In recent years, the aquaculture industry of seafood has been actively carried out for the purpose of efficiently securing marine resources. However, if the net used for this is immersed in the sea for a long period of time, the durability of the net itself may be impaired due to the attachment of fungi such as filamentous fungi, algae, molluscs, crustaceans, and shellfish, and Are blocked, seawater movement in the net is insufficient, leading to mortality of fish due to oxygen deficiency, facilitating bacterial reproduction, and nodaldia disease, crustacean caligsurisis due to worms belonging to Benedenia It is known to cause great damage due to diseases.

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. However, the drug can kill adherent organisms over a long period of time, that is, water. It is preferable that it has a low solubility in the body and that it has a property of being dissolved from the surface in very small amounts.

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

Conventionally, various compounds have been investigated in order to prevent these fishnet deposits. 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 when the antifouling composition is used, sufficient effects cannot be exhibited for a long period of time. 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 ingredients.
Bioaccumulation, human animal safety, and environmental pollution have begun to become problems. Further, for example, dithiocarbamates, which are organic sulfur compounds, are widely used as antifouling agent components like tin compounds. For example, Japanese Patent Laid-Open No. 51-
In Japanese Patent Publication No. 49227, manganese salt of ethylenebisdithiocarbamate is used as an antifouling component, which is mixed with a vehicle component to form a coating film on a fishing net to prevent organisms from adhering. Similarly, according to JP-A-51-51517,
A heavy metal salt of ethylene bisdithiocarbamic acid and a cellulose resin are mixed with a vehicle component to form a coating film on a fishing net to prevent organisms from adhering.

(Problems to be solved by the invention) From the viewpoint of various problems such as safety to human body and environmental pollution, metal salt of dithiocarbamic acid is regarded as the most desirable antifouling material component, but its effect persistence and efficacy In many cases, the stability cannot be fully satisfied. Therefore, an inorganic copper compound and an alkylenebisdithiocarbamic acid heavy metal salt are used as antifouling components, or other antifouling components,
Specifically, tin compounds are added. Therefore, there is a demand for a fishing net antifouling composition having a long residual effect period and less physical and chemical deterioration of the coating film.

(Means for Solving Problems) The present invention relates to a fishing net antifouling agent containing a lower alkylenebisdithiocarbamic acid heavy metal salt and HMT as essential components of the antifouling agent, and is safe for human livestock and fish. The purpose of the present invention is to provide a fishing net antifouling agent which has high properties, prevents adhesion and pollution that occurs on fishing nets, has a long residual effect period, and has little deterioration of fishing nets.

The lower alkylenebiscarbamic acid heavy metal salt usable in the present invention includes ethylenebisdithiocarbamic acid and propylenebisdithiocarbamic acid heavy metal salts such as zinc, manganese and copper, and ethylenebisdithiocarbamic acid to which a metal such as zinc and copper is coordinated. Examples thereof include manganese salts and cuprous-substituted ethylenebisdithiocarbamic acid heavy metal salts.

These can be added to the fishing net antifouling agent in the range of 1 to 50%, preferably 1 to 20%. And HMT is 0.01-2
A preferable result can be obtained by adding it in an amount of 0%, preferably 0.1 to 10%.

The antifouling component of the present invention is prepared by thoroughly mixing HMT in a slurry of a lower alkylenebisdithiocarbamate heavy metal, and drying and pulverizing the mixture into a vehicle, that is, a net dyeing component is kneaded at the same time and a good fishing net can be stirred. An antifouling composition is obtained.

If the lower alkylbisdithiocarbamate heavy metal is sufficiently pulverized, a good fishing net antifouling composition can be obtained by kneading and stirring the antifouling component and the net dyeing component at the same time. The fishnet antifouling agent of the present invention may be any known vehicle oil such as animal oil, vegetable oil, natural oil and fat, acrylic resin, vinyl resin, epoxy resin and alkyd resin. Naturally, it is possible to appropriately add auxiliary components such as a pigment, an extender pigment, a solvent, a solidification inhibitor, and the like to this paint component.

Furthermore, in addition to the antifouling material component of the present invention, known antifouling components and other pesticides can be optionally mixed and used 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 explain the present invention. The present invention is not limited to these specific examples.

Example 1 Finely ground ethylenebisdithiocarbamic acid zinc salt 15
Parts, HMT 1 part, acrylic resin 30 parts, xylene 54 parts,
Mix and stir.

Example 2 10 parts of finely pulverized manganese salt of ethylenebisdithiocarbamic acid, 1 part of HMT, 35 parts of acrylic resin, 54 parts of xylene are kneaded, mixed and stirred.

Example 3 15 parts of finely pulverized manganese salt of ethylenebisdithiocarbamic acid, 0.5 part of HMT, 30 parts of acrylic resin, and 54.5 parts of xylene are kneaded, mixed and stirred.

Example 4 15 parts of finely pulverized manganese salt of ethylenebisdithiocarbamic acid, 0.3 part of HMT, 30 parts of acrylic resin, and 54.5 parts of xylene are kneaded, mixed and stirred.

Example 5 15 parts of finely pulverized zinc-coordinated manganese salt of ethylenebisdithiocarbamic acid, 0.5 part of HMT, 30 parts of acrylic resin, xylene
54.5 parts are kneaded, mixed and stirred.

Example 6 Finely pulverized copper-coordinated ethylenebisdithiocarbamic acid manganese salt 15 parts, HMT 0.5 part, acrylic resin 30 parts, xylene
54.5 parts were kneaded, mixed and dispersed to obtain a paint.

Comparative Example 1 Prepared with 10 parts of ethylenebisdithiocarbamic acid manganese salt (product of Kumiai Chemical Industry Co., Ltd., "Mdaifer"), 35 parts of acrylic resin, and 55 parts of xylene.

Comparative Example 2 15 parts of ethylene bisdithiocarbamic acid zinc salt (product of Kumiai Chemical Industry Co., Ltd., "Differ"), acrylic resin
Prepare with 30 parts and 55 parts of xylene.

Comparative Example 3 10 parts of manganese salt of ethylenebisdithiocarbamic acid, 35 parts of acrylic resin and 55 parts of xylene were kneaded, mixed and stirred.

Next, the test results will be described.

Test Example A polyethylene fishing net was cut into a size of 1.00 × 50 cm, soaked in the antifouling agent of the present invention for 10 minutes, dried by air, and suspended in the sea within 2 m below the sea level to attach water organisms for 3 months. The results of the investigation are shown in the following table.

The criteria for the adhered area (state) are (1) no adherent organisms (2) adherent organisms of 5% or less (3) adherent organisms of 5 to 20% (4) adherent organisms of 20 to 50% Attached (5) Attached organisms 50% or more attached

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Claims (1)

[Claims] 1. A fishing net antifouling agent comprising a lower alkylenebisdithiocarbamic acid heavy metal salt and hexamethylenetetramine as essential antifouling material components in the fishing net antifouling agent.