JPS62142105A - Antifouling material - Google Patents

Abstract

PURPOSE:To obtain an antifouling material such as antifouling yarn, film, etc., having excellent antifouling property, nontoxicity and strength and capable of preventing the adhesion of algae and shell over a long period, by kneading powdery metal selected from copper, zinc, tin and their alloys together with graphite in a thermoplastic synthetic resin. CONSTITUTION:Powdery metal such as copper, zinc, tin, etc., or various alloys of said metals is mixed with graphite and the mixture is kneaded in a thermoplastic synthetic resin to obtain the objective antifouling material such as monofilament, joint yarn, twisted yarn, cord, net, film etc., free from toxicity to fish and capable of keeping the antifouling effect over a long period. The water-absorption of said resin is improved by the water-absorption of graphite to facilitate the dissolution of said metal powder preventing the sealing of the powder in the resin. The adhesion of the above aquatic life can be prevented by the effect of metallic ion generated from the dissolved metal powder.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to antifouling materials such as antifouling threads and films that are 1T5 resistant, nontoxic, and strong.

More specifically, the present invention relates to novel antifouling threads and films that are nontoxic to fish and can maintain antifouling properties for a long period of time.

<Prior art> Fish culture nets and fixed nets, which have become popular in recent years, require the fishing nets to be immersed in seawater for a long period of time.
Aquatic organisms such as Fujitbo attach to fishing nets and the ropes that make them, blocking the steel mesh, resulting in insufficient seawater movement, which adversely affects the survival of fish due to lack of oxygen, or reduces the durability of the ropes. decreases.

Particularly in Hamachi and Furi farming, the fish attach to the insects and suck blood, so the fish have the habit of rubbing them with a NQ net to remove them, but if the Fujibushi adheres at that time, the outer skin gets cut and the area becomes infected. Bacteria enters and causes a purulent disease, which then spreads and leads to mass mortality.

Moreover, at constant yt and tA, the increase in ocean current resistance causes poor net formation, and the increased weight makes it difficult to construct and pull up the net. For this reason, fishing nets are dipped in antifouling agents containing highly toxic copper compounds or tin compounds to prevent aquatic organisms from adhering to them. However, the antifouling effect of such an antifouling treatment agent is only for about 1 to 2 months, and therefore, no antifouling agent is known yet that completely satisfies the above requirements.

<Problems to be Solved by the Invention> Therefore, the present invention addresses the above-mentioned drawbacks of the conventional fishing net, and provides a net that is effective in eliminating aquatic organisms, harmless to fish, and maintains its antifouling effect for a long period of time. Aim to last.

Measures to solve these problems> In other words, metals with strong antifouling properties include copper, tin, zinc, or alloys of these metals, but most thermoplastic synthetic resins that are suitable for antifouling threads and films However, because these metal powders have a physical property of low water absorption, even if these metal powders are simply mixed in, only the metal powders exposed on the surface and around them will elute, and most of the metal powders will be encapsulated, resulting in a long-lasting antifouling property. will disappear.

By mixing carbon, that is, graphite, the physical properties of the thermoplastic synthetic resin are changed.

This improves the water absorption of the thermoplastic synthetic resin and
The purpose is to improve the dispersibility of the metal powder to be mixed so that the metal powder inside is eluted without being trapped.

The thermoplastic synthetic resin used may be polyethylene resin, polypropylene resin, or polyester, and other resins may be used as long as they have corrosion resistance against seawater and are suitable for monofilament and film. Of course.

The method for producing the antifouling yarn and film of the present invention is, for example, as follows.

Graphite in an amount of 0.3-2.0% by weight, preferably 1.5% by weight, and copper powder or copper alloy powder in an amount of 7-25% by weight are heat-kneaded to produce a pellet of a predetermined shape. This is heated, kneaded and extruded to about 180-220°C using an extruder, cooled, and then reheated and stretched to 90-100°C to produce a monofilament.

Next, add 1.0-2.5% by weight of graphite, preferably 1.8% by weight.
20-40% by weight, preferably 30% by weight of copper powder or copper alloy powder is mixed with thermoplastic polyethylene resin and heated and kneaded at about 170-210°C using an extruder to form a predetermined shape. Manufacture berets. This is extruded into a hot plate shape at about 180-220°C using an extruder, cooled, and then reheated and stretched at 90-100°C to produce a film.

Hereinafter, several examples of the present invention will be given and their results will be described. 8 History Kan 1-% ke 1 Atonement Stripe 01 Camphor Nera.

Example! The most important aspect of the present invention is to combine carbon, that is, graphite (hereinafter simply referred to as graphite) and copper powder or copper alloy powder, and to mix this into a thermoplastic synthetic resin.

A monofilament with a diameter of approximately 0.20+n was manufactured by mixing thermoplastic polyethylene resin with 1.0% graphite and 15% copper powder, and this was made into a 70-strand mesh with 30 wire meshes. This was cut into a test net with a width of about 1.2 m and a length of about 2 m. A weight was attached to this and it was suspended 1-3 meters below the sea surface. As a comparative example, 20% copper powder was added to thermoplastic polyethylene resin.
, produced a mixed monofilament with a diameter of 0.20,
This was knitted into a 30-n mesh having 70 twists. This was cut into a test net with a width of about 1.2 m and a length of about 2 m. A weight was attached to this and it was suspended 1-3 meters below the sea surface. The exam period is 3
The program lasted for 6 months and started in early March. The results are shown below. Efficacy was evaluated using the following stage codes depending on the occurrence of attached organisms.

As is clear from Table 1, when only copper powder is mixed, after the surface and surrounding copper powder is eluted, the internal copper powder is not eluted at all, and therefore the antifouling effect is completely lost.

Example 2 A drawn monofilament with a diameter of 0.2 m was manufactured using the following composition. This was knitted with 30 strands and 70 strands. This was cut into a test net with a width of approximately 1.2 m and a length of approximately 2 m. A weight was attached to this and it was suspended 1-3 meters below the sea surface. The test period was 36 months and began in early March.

(11 Graphite 1.0% in thermoplastic polyethylene resin,
5% copper powder (2) 2.0% graphite in thermoplastic polyethylene resin
%, copper powder 5% (3) Graphite 0.8% in thermoplastic polyethylene resin
%, copper powder 10% (4) Graphite 1.5% in thermoplastic polyethylene resin
%, copper powder 10% (5) 0.8% graphite in thermoplastic polyethylene resin
%, copper-tin alloy powder 15% (6) Graphite 1.2% in thermoplastic polyethylene resin
% PI'115% (7) Graphite 1.5% in thermoplastic polyethylene resin
% copper powder 15% (8) Graphite 0.3 in thermoplastic polyethylene resin
%↓Same powder 20% (9) 0.5 graphite in thermoplastic polyethylene resin
% copper) 20% QOI 1.0% graphite in thermoplastic polyethylene resin
% copper zinc alloy powder 20% α0 1.0% graphite in thermoplastic polypropylene resin
, 10% copper powder (2.0% graphite in 121 thermoplastic polypropylene resin)
%, copper powder lO% <131 1 graphite in thermoplastic polypropylene resin
．． 0%, copper, zinc alloy powder 10% α41 Graphite 2.0% in thermoplastic polypropylene resin.
0%, copper-tin alloy powder 10% [+51 1 graphite in thermoplastic polypropylene resin
．． 0%, copper'FI) 1 5%, a[O thermoplastic polypropylene resin, graphite 1
．． 5%, copper powder 15%, αη thermoplastic polypropylene resin, graphite 2.
0%, copper powder 15%, 0. graphite in thermoplastic polypropylene resin.
5%, copper powder 20%, 0! J 0 graphite in thermoplastic polypropylene resin
．． 8%, copper powder 20%, (to) IQ in thermoplastic polypropylene resin
Lead 1. .

%, 20% copper powder, 1.5% graphite in thermoplastic polyester resin,
1. Powder 10% (Foundation) 2.0% graphite in thermoplastic polyester resin
, 2 Same powder 10% ■ 1.5% graphite and 15% copper powder in thermoplastic polyester resin 2.0% graphite in thermoplastic polyester resin
, 15% copper powder @ 0.5% graphite, 20% copper powder in thermoplastic polyester resin 1.0% graphite, 20% copper powder in thermoplastic polyester resin Graphite in thermoplastic polyester resin 1.0%, copper, zinc alloy powder 20% @ 20% copper powder in thermoplastic polyethylene resin (up to)
20% copper powder in thermoplastic polypropylene resin Sections fil to 1 are the compositions of the present invention, and 20% to 2 are commonly used compositions.

(Left below) Table 2 Table 2G Selling) Efficacy was determined in the same way as Table 1 based on the occurrence of deposits.

Effect> As is clear from Table 2, it was found that the antifouling effect differed depending on the mixing ratio of graphite and copper powder. It was also found that there is almost no difference in the antifouling effect when the amount of copper powder mixed is 15% or more.

It has also been found that there is almost no problem with regard to strength when the amount of copper powder is within 20%.

Example 3 A film having a width of about 1 m and a thickness of about 2 mm was manufactured using the following composition. This is about 0.8 m wide and about 1.3 m long.
A test film was prepared by cutting the film into a length of 50 m. Attach a weight to this 1 below sea level
-Hanged at 3m. The test period will be 36 months, and 3
I went from the beginning of the month.

+11 Graphite 1.0 in thermoplastic polyethylene resin
%, copper powder 20% (2) 1.5% graphite in thermoplastic polyethylene resin
;、;、25% copper powder (3) 2.0% graphite in thermoplastic polyethylene resin
%, copper powder 30% (4) Graphite 1.5% in thermoplastic polyethylene resin
%, copper zinc alloy) 30% (5) Graphite 1.5% in thermoplastic polypropylene resin
(6) Graphite 2.0% in thermoplastic polypropylene resin.
(7) Graphite 2.0% in thermoplastic polypropylene resin.
0%, copper, warm alloy powder 30% (8) Graphite 1.5% in thermoplastic polyvinyl chloride resin
, i.e.) 25% (9) Graphite 2.
0%, copper powder 30% θω Graphite 2.0 in thermoplastic Aμ-→vinyl th resin
%, copper, warm alloy powder 30% Qll 2 Copper powder 50% in plastic polyvinyl chloride resin
% θ21 Copper powder 40% in thermoplastic polypropylene resin
%(1)~lot is the composition according to the present invention, and 0υ~@ is the comparative formulation.

Table 3 Efficacy was judged in the same way as Table 1-2 depending on the occurrence of deposits.

<Effects> The anti-lη effect of the film produced by the production method of the present invention is clear from Table 3. In comparison, in the case of 0υ-beating in which only copper powder is mixed, the antifouling property is lost even if the amount of copper powder is increased.

It was also found that there was almost no difference in antifouling efficacy between copper powder and copper-tin alloy powder. It was also found that when the amount of copper powder was 30% or more, there was almost no difference in the anti-Iη effect. In addition, regarding strength, in the case of film, the amount of copper powder is 30%, and the amount of graphite is 30%.
．． It was also found that there was no problem at all within 0%. Furthermore, the present invention provides antifouling threads and films that show no deterioration in physical properties in seawater over a long period of time and are excellent in antifouling properties, non-toxicity, and strength.

2.5. ′−

Claims (3)

[Claims] (1) Graphite and metal powder such as copper, zinc, tin, or various alloys of these metals are mixed and kneaded into thermoplastic synthetic resin, and the dispersibility of graphite allows the metal powder to be dispersed. The water absorbency of graphite improves the water absorption of thermoplastic synthetic resin, and the effect of metal ions released from the metal powder causes algae,
Or, an antifouling material characterized by preventing the occurrence of adhesion of shellfish. (2) Thermoplastic synthetic resin is monofilament, connecting thread,
The invention according to claim 1, which is a twisted yarn, a rope, a net, etc. (3) The antifouling material according to claim 1, wherein the thermoplastic synthetic resin is a film.