JPS5927806A - Polyvinyl alcohol (pva) type fishery material having repellency against organism - Google Patents

Abstract

PURPOSE:A safe polyvinyl alcohol (PVA) type fishery material, prepared by incorporating a copper compound exhibiting a specific solubility in water in a specific amount with hydrophilic PVA type synthetic fibers or molded articles thereof, and having the lasting repellency against organisms. CONSTITUTION:A polyvinyl alcohol (PVA) type fishery material, prepared by incorporating 1-50wt%, based on PVA, copper compound, e.g. cuprous oxide, cuprous sulfide, copper pyrophosphate, copper thiocyanate and/or copper cyanide, exhibiting <=1.0g/100g water solubility in water at 20 deg.C, preferably cuprous oxide or/and copper thiocyanate, in PVA type synthetic fibers having 5-25% swelling degree, obtained by dipping in water at 30 deg.C for 48hr, and defined by the formula or molded articles thereof, capable of permanently preventing the adhesion and breeding of marine organisms, and usable for fishing nets, ropes or sheets, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to materials used for fisheries, such as fishing nets, ropes, and sorting. Use of polyvinyl alcohol (hereinafter abbreviated as VA) synthetic fibers or repellent fibers or molded products mixed with molded products.

Things that are used during the fishing season in the ocean, such as ships, fishing nets, ropes, and construction sheets, have been observed to attract and breed organisms, causing various problems. Totohe is a place where marine life□Animals such as barnacles, celluloids, bryozoans, and molluscs, and other substances such as brown algae and green rocks□ adhere to the bottom of a ship while it is sailing or anchored. The creature cannot be separated from it unless a significant external mechanical force is applied.

It is said that when marine organisms adhere to the bottom of a ship, the following problems occur: (1) The frictional resistance between the seawater and the ship's hull increases, reducing the ship's speed, resulting in increased combustion. It will be up.

+2) Cost of removing j1 kimono and decrease in operating income during that time.

(3) Rei no 3 no Mikoto,), νsmall.

Anti-fouling paint on the bottom of the ship that prevents the attachment of marine organisms [
7. Those containing cuprous oxide are generally used. Father - About power fishing nets, ropes, etc. tl/1 h of epiphytes
L;, Changes in tidal currents due to length and breeding (・1' Increase in weight of fishing nets and ropes, and breakage of fishing nets and ropes・','J
ij! becomes.

Therefore, when adhering 1), as a countermeasure 7), treat with tin (L7) or combine the copper compound with hydrophilic 1 binder or hydrophobic 1' binder 2 Shikawa L7. <Methods are being taken. By the way, organic tin has pollution problems and processing costs are relatively high. If the flow velocity IW is excessive, the initial effect is great, but the effect is not permanent.When treating ropes and ropes using a hydrophobic binder, copper compounds on the surface of the binder are washed out, but What's inside doesn't elute, so there's almost no binding effect, but it does increase by 1 degree.Currently, there are no good binders available, and when they are used, the nets and ropes harden and even workability deteriorates. As for fibers made of steel, copper-containing acrylic fibers are known as conductive fibers.In other words, the stiffness is reduced by adsorbing copper ions to the acrylic fibers and then reducing the stiffness of the fibers by using a reducing agent. Metallic copper is reduced and precipitated within the fibers, and the copper grains are extremely small.The surface of acrylic fibers is porous, so if such fibers are placed in seawater, copper ions such as V will be released in the seawater. In the initial stage of application: a large amount of bath water is exhausted, preventing the adhesion of marine organisms and the long-lasting effect of 12 cannot be expected.Furthermore, copper wire or copper-plated fibers have poor processability as textile products. When it is initially put into the ocean, it is effective in preventing marine organisms from attaching to it, but as the copper corrodes, its effectiveness decreases, and as the corrosion progresses, W4?IM, etc., fall off and the effect is not permanent.

In other words, at present, no practical marine materials that are safe and have a permanent repellent effect have been proposed.

The present invention of the water tile tool tool was made in view of the above points, and relates to a rice scoop for water tiles made of fibers or molded articles made of hydrophilic and swellable PVA mixed with a button compound. However, P specified for the persistence of the effect
The intended purpose was achieved by combining the copper compound designated as vA with A11-1.

That is, the present invention incorporates a copper compound having a solubility in water of 1.0f7100ii' or less at 20°C into PVA-based synthetic fibers or molded articles whose concentration is 5 to 25% when immersed in water at 30°C for 48 hours. This is a fishery material using a PVA-based synthetic fiber or a molded product having repellency obtained by mixing 1 to 50% by weight of PVA.

It should be noted that the subject material of the present invention is not limited to fibers, but includes molded products such as films, but the following description will be made regarding fibers to avoid complexity. Since PVA-based synthetic fibers are hydrophilic fibers, materials with different degrees of swelling can be selected depending on the manufacturing conditions. In other words, if the hot drawing ratio is increased during the manufacturing process, and further acetalization is performed as necessary, the degree of swelling of the resulting fiber tends to decrease, but under normal manufacturing conditions, wet PVA synthetic fibers If the swelling degree is about 20%, dry PV
A-based synthetic fibers have a swelling degree of approximately 10%, and the present inventors focused on the bond between such moderately swellable PVA-based synthetic fibers and the copper compound that gradually dissolves into water. be. As a result of studies conducted by the present inventors, in order for copper compounds to be gradually eluted from PVA-based synthetic fibers mixed with copper compounds, the degree of swelling must be between 5% and 25%. Understood. As a result, the elution of the copper compound is permanent, and the effect of preventing the adhesion of marine organisms can be maintained for a long time. Even if it were possible to mix a copper compound with hydrophobic fibers (nylon, polyester, polyethylene, polypropylene, polyvinylidene chloride, etc.), such fibers are hydrophobic and will not swell when put in water, so the copper compound is not suitable. Cannot be eluted. -Rayon, which is actually a hydrophilic fiber, uses caustic soda and sulfuric acid during its manufacturing process, which causes severe elution of copper compounds and poor copper compound yield. Furthermore, since rayon has a high degree of swelling, the elution rate of the copper compound is high, and the durability of the effect is poor, and the strength of the fiber itself is low.

In other words, PVA-based synthetic fibers with a swelling degree of 5% to 25%, more preferably 15%, are optimal in order to gradually elute copper compounds and maintain the effect of preventing the adhesion and proliferation of marine organisms. Understood.

The copper compound to be mixed next has a high solubility, which causes a chelate bond when mixed with PVA for spinning, resulting in poor spinnability. Various studies were conducted regarding solubility, and the following results were obtained. That is, it is necessary that the copper compound exhibits a solubility of 1.0y/1002 water or less at 20°C. Substances that satisfy this condition include cuprous oxide, cuprous chloride, silver pyrophosphate, copper thiocyanide, and copper thiocyanide, and it has been found that cuprous oxide and copper thiocyanide are particularly optimal.

Also, a plurality of these compounds may be used. Regarding the addition of the above-mentioned copper compound to PVA-based synthetic fibers, according to experiments by the present inventors, for example, when considering process passability (workability) during net making, the dry knot strength is 2. .0r
/d, problems such as thread breakage occurred during net making. Therefore, considering process passability, it was found that the maximum kneading ratio of the copper compound is 50% by weight relative to PVA. On the other hand, if the kneading ratio of the copper compound is too small, the desired repellency effect will be lost even if there is no problem with process passability. Therefore, the amount of damage that lasts for more than half a year is at least 1% compared to PVA.
It has been found that it is necessary to incorporate % by weight. The present invention will be further explained in the following examples.

Example 1 PVA with a moisture content of 45% (degree of saponification 99%, degree of polymerization 170)
0) Mix 10 parts of cuprous oxide powder with 100 parts of 2
．． □Spun raw yarn spun using a 5-inch extruder
Stretching ratio: 6 times, heat shrinkage: 25 at furnace temperature of 20-240℃
% and the following results were obtained.

Single fiber strength and elongation 5.6 f/d x 16
．． 3% dry knot strength 3.2 r/d hot water shrinkage rate (100℃ x 30 minutes) 7.4% swelling degree
10.6 Copper content (based on pure copper) 7.9% A rope was made using this PVA-based synthetic fiber, and the rope was installed in the sea to examine its repellency to marine life.
The elution of ■11 copper oxide continued during the month, and the adhesion of marine organisms was extremely low compared to ordinary PVA-based synthetic fiber ropes that do not contain cuprous oxide.

Example PVA concentration 15% (degree of saponification 99, degree of polymerization 1700)
Copper thiocyanide powder was mixed in a water bath solution at a ratio of 20% to PVA, and wet spinning was performed to obtain the following yarn.

Single fiber strength elongation y 6.7 f/d x 9
．． 6% dry nodules strong 4.9? /d Hot water shrinkage rate (100°C x 30 minutes) 4.2% swelling degree
23.5% Copper content (based on pure copper) 9.8% A rope was made using the obtained PVA synthetic fiber and commercially available polyester fiber, set in a wooden frame, and floated on the sea surface. We investigated the repellency of marine organisms. In the case of this example as well, thionanide steel continued to be leached out even 9 months after installation, and there was very little adhesion of marine organisms.

Patent applicant: Rishi Co., Ltd. Agent: Patent Attorney Ken Honda

Claims (1)

[Claims] (]) Polyvinyl alcohol fiber (XJ) is a material for marine products made of a molded product, which has a degree of swelling defined below of 5 when immersed in water at 30'C for 48 hours. ~2
1.0 at 20°C in polyvinyl alcohol fibers or molded products. //Polyvinyluer A-coal-based fisheries river with biorepellent properties made by mixing 1 to 50% by weight of s-11 in +l IJ vinyl alcohol with a copper arsenide having a solubility of less than 100f in water. Quality material. (l) (2) The copper compound is one or more selected from cuprous oxide, cuprous sulfide, pyrophosphate steel, thiocyanide, cyanide i'ii; A polyvinyl alcohol-based fishery material having biorepellent properties as described in claim (1).