JPS6135014Y2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to marine materials, and more specifically to marine materials having a biofouling prevention effect.

Marine materials such as fishing nets, ropes, and marine structures that are generally used in the sea have attached to them living things such as shellfish such as mussels and barnacles, ascidians, polychaetes such as staghorn, and algae such as sea lettuce, blue seaweed, and seaweed. Fishery materials with living organisms attached to them lose their buoyancy or become damaged due to increased resistance to tidal currents. In addition, in the case of aquaculture nets, many problems have been pointed out, such as the attachment of organisms that restricts the flow of water and deteriorates water quality (oxygen deficiency). Therefore, attempts have been made for a long time to prevent organisms from adhering to marine materials, and many proposals have been made. For example, Japanese Patent Publication No. 38-5422 uses organic tin-based compounds, Japanese Patent Publication No. 40-21426 uses organic tin-based polymers, and Japanese Patent Publication No. 45-9670 uses tetrachloroisophthanitrile, which have antifouling properties. Various compounds have been proposed.

However, these proposals involve eluting a portion of the compound used in minute amounts, and preventing the adhesion of shellfish and algae due to the toxicity of the eluted substances, which may contaminate the ocean or have a negative impact on fish. There is a problem that it causes

In order to improve these drawbacks, several antifouling methods using nearly non-toxic substances have also been proposed. Specifically, Japanese Patent Publication No. 53-10778 discloses a method of smoothing the surface and coating the surface with a releasable substance to reduce surface tension, while Japanese Patent Publication No. 55-6607 discloses methods such as mica group minerals, montmorillonite group minerals, etc. JP-A No. 55-108225 proposes a method using fluororesin fibers, but both methods have the disadvantage that they have little effect on preventing biofouling.

Furthermore, Japanese Utility Model Publication No. 53-39673 proposes a wire mesh tool for cultivating fish and shellfish in which a wire mesh is flocked with water-resistant and corrosion-resistant short fibers to form a raised surface on the entire surface of the wire mesh. However, this method has little effect on preventing biofouling. In addition, the wire mesh tends to corrode and has a durability problem, and the flocked short fibers tend to peel off because the adhesiveness between the flocked short fibers and the wire mesh is not sufficiently improved.

In view of the current state of conventional technology, the inventors of the present invention have conducted extensive studies on methods that can substantially increase the antifouling effect without using toxic substances and maintain the antifouling effect for a long period of time, and have developed the present invention. It has been achieved.

The present invention is a fishery material made of a synthetic resin, on which short fibers substantially made of synthetic fibers are flocked, and a silicone resin or a fluorine resin is attached to the surface of the short fibers. be.

The present invention will be explained in detail below.

In this invention, marine materials made of synthetic resins are fishing nets such as fixed nets and aquaculture nets, ropes for mooring ships and marine structures, fishing nets, floating fish reefs, floating breakwaters, aquaculture reeds, large buoys, etc. Refers to structures, etc.

In addition, in this invention, the synthetic resin is nylon.
6. Polyamide resins such as nylon-66 and nylon-12, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene and polypropylene, polyvinylidene chloride, polyvinyl chloride, polystyrene, ABS resin, glass Refers to fiber-reinforced epoxy resin, phenolic resin, etc. Fishery materials made of synthetic resin have advantages over those made of metal, such as being lighter, less susceptible to corrosion, more durable, and cheaper. However, like metal, it has the disadvantage that various marine organisms tend to adhere to it.

In the present invention, short fibers made of substantially synthetic fibers flocked on the surface of marine materials made of synthetic resins are polyamide resins such as nylon-6 and nylon-66, and polyester-based fibers such as polyethylene terephthalate and polybutylene terephthalate. Short fibers are made of fibers, polyolefin fibers such as polyethylene and polypropylene, polyvinylidene chloride fibers, polyvinyl chloride fibers, acrylonitrile fibers, etc. Among these, natural fibers such as cotton and wool are used for the purposes of this invention. It is okay to have some mixture as long as it does not deviate.

The short fibers of the present invention preferably have a fiber length of 0.3 to 8 mm and a fiber diameter of 0.01 to 0.1 mm. In particular, short fibers with a fiber length of 1 to 6 mm and a fiber diameter of 0.01 to 0.04 mm are preferred. More preferred. The cross-sectional shape of the short fibers may be circular, hollow, polygonal such as a triangle, or irregularly shaped such as a gourd shape.

It is preferable that the short fibers to be flocked on the surface of the marine material are almost uniformly flocked on the surface of the marine material. It is undesirable that the flocking density is quite uneven and that there are areas where no flocking occurs.

In this way, short fibers made essentially of synthetic fibers are flocked onto the surface of marine materials made of synthetic resin, which has a slight biofouling prevention effect, that is, an antifouling effect, but it is difficult to reduce the negative effects of biofouling. I don't need it. However, the length and thickness of the short fibers to be flocked are selected within the above range, and silicone resin or fluorine resin is attached to the short fibers before or after flocking to cover the surface of the short fibers. When the appropriate amount of material is coated, plankton-like organisms will initially adhere to the fishery material, but once the adherent organisms grow a little, the attached organisms will peel off and have a substantial antifouling effect. Effect is 2
It has been found that this effect can be achieved over a long period of time, for more than a year.

Examples of silicone resins to be attached to short fibers include dimethylpolysiloxane, methylphenylpolysiloxane, methylvinylpolysiloxane, trifluoropropylmethylpolysiloxane, amine-modified polysiloxane, and alkylaryl-modified polysiloxane. Preferably, it is not oil-like or grease-like, but rubber-like and has a molecular weight of 10×10 ⁴ or more. These resins are preferably applied to short fibers in the form of a dispersion or emulsion. Further, the applied silicone resin may be applied to the short fibers in an uneven manner, but it is preferable that the applied silicone resin be applied almost over the entire surface.

Examples of fluorine-based resins to be attached to short fibers include polytetrafluoroethylene, copolymers containing tetrafluoroethylene as a main component, polyvinylidene fluoride,
Examples include polyvinyl fluoride and polychlorotrifluoroethylene, but these are preferably applied to short fibers in the form of a dispersion or emulsion.

The amount of silicone resin or fluorine resin applied to the short fibers is preferably 1.0% by weight or more and 30% by weight or less. This is because if it is less than 1.0% by weight, the antifouling effect will be small, and if it is more than 30% by weight, sticking between short fibers will likely occur, and the antifouling effect will be reduced. As the resin to be attached to the short fibers, silicone resin is more preferable than fluorine resin from the viewpoint of antifouling effect.

The marine materials of the present invention have the following advantages compared to conventional materials for preventing biofouling.

(1) It is non-toxic and has no leachable substances, so it does not pollute the ocean or worsen the marine environment.

(2) Since it is non-toxic and contains no leachables, it will not have a negative impact on the growth of fish and shellfish.

(3) Since it has a great antifouling effect, it will not have any negative impact on fish and shellfish due to lack of oxygen during aquaculture.

(4) Conventional antifouling materials can only provide a short-term antifouling effect, but the material of the present invention has a long-term antifouling effect.

(5) Since it has a large antifouling effect, it does not cause a decrease in buoyancy due to biofouling, making it easy to design marine structures.

(6) Since it has a large antifouling effect, there is no increase in tidal current resistance due to biofouling, and the durability of marine materials can be improved.

Hereinafter, the present invention will be explained with reference to the accompanying drawings.

FIG. 1 is a side view showing an example of the fibrous marine material according to the present invention. Short fibers 2 made of synthetic fibers are flocked to a rope-like material 1 made of synthetic fibers, and silicone resin or fluorine resin is attached to the surface of these short fibers 2. Such fibrous materials have the effect of preventing biofouling and are therefore useful in fields such as fishing nets and mooring ropes.

FIG. 2 is a side view of the structural marine material according to the present invention. Short fibers 2 made of synthetic fibers are flocked to the pipe-like article 3 made of synthetic fibers, and silicone resin or fluorine resin is attached to the surface of the short fibers 2. Such a pipe-like object 3
Because it has the effect of preventing biofouling, it is useful as a member of marine structures such as floating fish reefs, floating breakwaters, and aquaculture reeds.

FIG. 3 is an enlarged side sectional view of short fibers in the flocked portion of the marine material of the present invention. Short synthetic fibers 4
A coating 5 of silicone resin or fluorine resin is adhered to the surface to provide an effect of preventing biofouling. It is preferable that this coating substantially covers the entire exposed surface of the short fibers 4 from the viewpoint of preventing biofouling.

FIG. 4 is a side view showing another example of the fibrous marine material according to the present invention. The net-like material 7 is a rope-like material 6
One end of the net is supported by a net, and short fibers 2 whose surfaces are coated with a silicone resin or a fluorine resin are flocked to such a net or rope 7. Such marine materials have a great effect on preventing biofouling, so they are useful for nets that are immersed in the ocean for a certain period of time, such as fixed nets and aquaculture nets.

Fig. 5 is a side view showing an example of a marine material related to the structure of the present invention. That is, Fig. 5 shows a floating breakwater 8, which is made of short fibers 2 with silicone resin or fluorine resin attached to the surface.
are planted on the pipe-like bodies 3 and block-like bodies 9 which are the constituent members of the floating breakwater 8. Since almost no living organisms attach to such a floating breakwater 8, the balance of buoyancy does not deteriorate over time, and resistance to tidal currents does not increase, so there is an advantage in that it is highly durable.

Example Six polyethylene terephthalate yarns (1000 denier, 192 filaments, IV = 0.88) were combined, and this yarn was first twisted with a first twist coefficient of 1500.
Three of these threads were combined and twisted to create a twisted thread of approximately 20,000 denier. On the other hand, a pipe with an inner diameter of 100 mm and an outer diameter of 130 mm was made using a pipe forming machine using nylon-6 (relative viscosity 3.4) at an extrusion temperature of 260°C.

An acrylic adhesive (Teisan Resin-EXP910) is applied to this twisted yarn and pipe, and polyethylene terephthalate cut fiber (fiber length 3 mm, fiber diameter 0.03 mm) is applied to this adhesive-coated twisted yarn and pipe under high voltage (approximately 80 kv). Hair transplanted in the dryer, then in the dryer
It was treated at 130°C for 10 minutes. The twisted yarn and pipe treated with flocking in this way and the twisted yarn and pipe without flocking were immersed approximately 1 m below the sea surface and the state of biofouling was investigated. 3 months after soaking
As a result of investigating the status of biofouling after 6 months, 1 year, and 2 years, it was found that the non-flocked items had a lot of shellfish and algae attached during all immersion periods, while the flocked items had a lot of adhesion of shellfish and algae. Almost no biofouling was observed.

[Brief explanation of drawings]

FIG. 1 is a side view showing an example of the fibrous marine material according to the present invention, FIG. 2 is a side view illustrating the structural marine material according to the present invention, and FIG. 3 is a flocked portion of the marine material according to the present invention. Enlarged side cross-sectional view of short fibers in
FIG. 4 is a side view showing another example of the fibrous marine material according to the present invention, and FIG. 5 is a side view illustrating the marine material related to the structure according to the present invention. 1, 6: Rope-like material, 2, 4: Short fiber, 3: Pipe-like material, 5: Resin coating, 7: Net-like material, 8: Floating wave bank, 9: Block-like material.

Claims (1)

[Scope of utility model registration request] Fishery materials made of synthetic resin, in which short fibers made of synthetic fibers are flocked on the surface of the materials, and the surfaces of the short fibers are coated with silicone resin or fluorine resin.