JPH01308205A - Repellent material of underwater organism and material preventing attaching of underwater life - Google Patents

Abstract

PURPOSE:To obtain a repellent material of underwater organism having excellent prevention of attaching of underwater life, especially seaweeds and shellfishes, and a material preventing attaching of underwater organism made of said repellent material, comprising specific polyvinyl alcohol-based resin having bloating tendency by water. CONSTITUTION:A repellent material of underwater organism, gelled in water and any underwater organism is repelled, easily moldable, having high certainty and effect in a long period of time, thus damage by underwater organism is steeply reduced, is obtained from polyvinyl alcohol-based resin having 80-99mol%, especially 87-95mol% saponified degree and bloating tendency by water. Furthermore, said resin, preferably at least two resins or yarns having different saponified degree are set on at least the surface (exemplified as 2-4) of a constructed matter 1 such as fishery rope, net or float, thus a material preventing attaching of underwater organism capable of preventing attaching of underwater organism in a long period of time.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a repellent material that is excellent in preventing adhesion of aquatic organisms, particularly seaweeds and shellfish, and to aquatic materials made from the repellent material.

[Prior Art] Conventionally, underwater structures with seaweed and shellfish attached to them, such as fishing ropes, cotton, and floating bodies, tend to have aquatic organisms attached to them, resulting in an increase in weight, causing the structures to sink and become unusable. The damage caused by the inability to do so was enormous.

[Problems to be Solved by the Present Invention] However, the reality is that there is still no solution to the problem of adhesion of seaweed and shellfish.

In view of such prior art, the present invention was achieved by investigating that a specific resin has an effective effect on these seaweeds and shellfish.

In other words, it has been discovered that a gel-like substance made of a specific polyvinyl alcohol resin effectively blocks the attachment of these animals and plants.

[Means for Solving the Problems] That is, the present invention provides (1) a water-soluble resin having a degree of saponification of 80 to 99 mol% and comprising at least a water-swellable polyvinyl alcohol resin; Biological repellent.

2) An aquatic organism characterized in that a polyvinyl alcohol resin having a saponification degree of 80 to 99 mol% and a pA navy blue made of the polyvinyl alcohol resin having at least water swelling properties is present on at least the surface of the construct. A” Anti-dish material.

(3) The material that prevents aquatic organisms from landing on the material according to claim (2), wherein the resin is composed of at least two types of resins having different degrees of saponification.

The polyvinyl alcohol resin of the present invention having a degree of saponification of 80 to 99 mol% and the fibers made of the resin have the characteristic of becoming a gel-like substance in water. The present invention is based on the discovery that such a gel-like substance has a repellent effect on aquatic organisms.

The aquatic organism repellent material of the present invention is selected from a polyvinyl alcohol resin having a degree of polymerization of at least 15oo, preferably 2000 or more, and more preferably 2500 or more.

Such a resin has a degree of Gunnification of 80 to 99 mol%, preferably 85=-95 mol%, more preferably 87 to 9 mol%.
5 mol% is selected from the viewpoint of moldability, or
Such resins have a low degree of polymerization and have a high gelation rate in water, and depending on the application, it may be preferable to use a combination of these resins. The gel-like substance of such a resin acts suitably as an aquatic organism repellent.

The gelling behavior of this resin varies whether it is formed into a fibrous material or a molded product, and exhibits the same gelling property. It is preferable to select the degree of saponification depending on the conditions such as the place of use, since it becomes easier to dissolve in water with a low degree of saponification.

When this resin or fiber is kept under tension so that water cannot penetrate into it, it has a high shape retention property and can prevent dissolution, but when it is kept in a relaxed state, it causes dissolution. In addition, gelled resin remains in a gel state for quite a long time, and remains that way until it is dispersed by external forces such as waves or currents, so these properties can be skillfully utilized. We provide a repellent material that maintains its repellent effect for several months to several years.

The resin of the present invention can be easily made into fibers by stretching, and when stretched at a high stretching ratio, the resin has a tensile strength of 10 Md or more, a roughness (15 Md or more, an initial elastic modulus of 150 Md or more, Furthermore, it provides fibers with excellent physical properties of 250 g/d or more.

In the present invention, it is important to gel in water, and it is necessary to select a material that dissolves in water.

Such properties of the resin of the present invention are even more pronounced in high temperature water. Therefore, if necessary, the surface can be brought into a gel state by immersing it in hot water. The present invention skillfully utilizes this unique property.

Fibers with such high physical properties are produced by dissolving such polymers in DMS○ of p116-8 to make a spinning solution, which is then discharged from the spinning machine into an inert atmosphere (air, nitrogen, helium, etc.) and introduced into a coagulation bath. do. This coagulated thread has a diameter of 180 to 230
It is obtained by stretching in a heated gas of 'C to a total stretching ratio of 10 times or more, preferably 12 times or more, and further still 15 times or more. Such fibers can also be coated with the same resin or another water-soluble resin.

In addition, the polyvinyl alcohol resin can be used as a solvent solution,
It can also be directly applied to the surface of the object to be treated.

For example, a fiber is formed from a resin with a saponification degree of 90 mol%, and a fiber fabric made of these fibers is coated with a resin with a saponification degree of 85 mol% in a lattice shape or polka dot shape (including dotted shapes). When coated in a similar manner, the timing of gelation can be delayed and a product that acts as an aquatic organism repellent for a long period of time can be provided. In this case, the resin with a saponification degree of 88 mol% gels within a few minutes after being immersed in water, and after several days the resin has a saponification degree of 9.
The surface of the 5 mol% fibers begins to gel. The gelled part at this time is the part that is in contact with water from the beginning, and the next gelled part is the part coated in a pattern with a saponification degree of 88.
The fiber surface area after mol% of the resin portion has dissolved and disappeared. With such a structure, it is possible to prevent aquatic organisms from attaching for a considerable period of time. Such a resin film, for example, a plurality of layers of the resin film with a degree of saponification of 85 mol%, a plurality of layers of the resin film with a degree of saponification of roughly 95 mol%, or a combination of these resin films and fibers. By employing a structure such as a cap-matching system, aquatic organisms are repelled for a desired period of time. be able to.

The materials used in the present invention refer to materials for parts and general structures that are used by being immersed in water (seawater) or have at least a partially immersed part, and include fishing gear, fishing nets, mooring lines, and tow lines. , ships, reefs, floating bodies, piers, shore banks, breakwaters, bridge girders, marine stations, and other various structures, as well as the materials that make up these structures.

The fibers only need to have the polyvinyl alcohol resin or fibers as a sheath on the surface, and any material may be used for the core. For example, high-strength polyethylene fibers, polyacrylonitrile fibers, aramid fibers, etc., which have a fiber strength of 15(]/d or more and an initial elastic modulus of 250 g/d or more, can be arranged in the core. The covering material is not limited to fibers, and may be any material to which aquatic organisms may adhere, such as concrete, steel, wood, plastic, etc.

The present invention will be explained with reference to the drawings.

FIG. 1 shows the construction member (
This figure shows an example of a cross section of a plate-like object, in which a polyvinyl alcohol resin film 2 with a degree of saponification of 90 mol% is laminated on the surface of a construction member 1.

The film 2 may be made of fibers made of the polymer, or may be a structure made of the fibers as raised fibers.

Fig. 2 shows a fabric-like material made of polyvinyl alcohol resin fibers 3 with a saponification degree of 96 mol% attached to the surface of a construction member 1, and a dot-shaped polyvinyl alcohol resin with a saponification degree of 89 mol% on the surface of the fabric. A coating film 4 is provided. The entire surface of this structure may be further coated with a polyvinyl resin film having a degree of saponification of 88 mol %, for example, or only the coating film 4 may be coated.

Preferably, these constructs are colored, for example green, brown, preferably dark colored.

The present invention will be further explained below with reference to Examples.

[Example] Example 1 A film made of polyvinyl alcohol resin with a degree of saponification of 93 mol% was laminated on the surface of a rope, a raised fabric was formed with fibers made of the resin with the degree of saponification mentioned above, and this was applied to the rope. Two coated structure ropes were formed that were attached to the surface.

These ropes were left submerged 1 m underwater in the summer. At the same time, the rope base material itself, which was not used as a covering structure for comparison, also sank.

Two months later, when these ropes were pulled up and observed, the ones with only the rope base material had a large amount of algae and shellfish attached to them, but the resin-coated ropes had no algae or shellfish attached to them. It wasn't.

It has been found that the coated structure rope having raised naps naturally gels and becomes fixed to the resin film while the naps are present, and this exhibits a high algae-proofing effect.

Example 2 Consisting of two types of polyvinyl alcohol resins with a saponification degree of 87 mol% and a saponification degree of 94 mol%. With the structure of covering the former net-like material, a covering structure rope was formed by laminating it on the surface of the rope.

This rope was left submerged 1 meter underwater in the summer. When observed after 6 months, neither algae nor shellfish were attached to the rope.

Water this rope in the laboratory! When immersed in a constant temperature bath at 40°C and observed the gelation and dissolution state, the network first gelled, and then the water-contact resin surface with a saponification degree of 94 mol% (from the beginning of the mesh area of the network) (parts in contact with water) began to gel.

After several hours, the net-like material was dissolved and erased, and the portion of the resin film with a degree of saponification of 94 mol % where the net-like material was present was exposed to water. After several hours, the resin film began to gel, and after another few hours, it was dissolved and disappeared.

As a result of this experiment, it was found that such a laminate exhibits the effect of sustaining the repellent effect for a longer period of time compared to a covering structure made of a single component.

[Effects of the Invention] The aquatic organism repellent material of the present invention uses a specific resin that gels in water, and uses the gel-like substance to repel aquatic organisms, and is easy to process, highly reliable, and has a long lifespan. Since it is effective over a period of time, the damage caused by conventional aquatic creatures can be greatly reduced.

In addition, such repellent materials can be easily attached or applied to the surface of structures, and can prevent aquatic organisms from adhering to them for a long period of time, so they can be used not only as marine materials, but also for civil engineering and architectural structures. validly applied to

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram illustrating an example of a construction member of a marine material for preventing the adhesion of aquatic organisms to a car to which the aquatic organism repellent material of the present invention is attached. FIG. 2 is a schematic diagram showing an example of another construction member. In the figure 1: Construction member 2: Polyvinyl alcohol resin film (repellent material) 3: Polyvinyl alcohol resin fiber (repellent material) 4: Polyvinyl alcohol resin coating film (repellent material)

Claims (3)

[Claims] (1) An aquatic organism repellent material having a degree of saponification of 80 to 99 mol% and comprising at least a water-swellable polyvinyl alcohol resin. (2) An underwater biofouling prevention material characterized by having a degree of saponification of 80 to 99 mol% and at least a water-swellable polyvinyl alcohol resin or fibers made of the resin existing on at least the surface of the construct. . (3) The aquatic organism adhesion prevention material according to claim (2), wherein the resin is composed of at least two types of resins having different degrees of saponification.