JPH0671786B2 - Method for producing algae-proof marine product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a method for producing a marine product having excellent algae resistance.

More specifically, the present invention relates to a method for producing a marine material such as a net-shaped material and a rope-shaped material having excellent algae-proof property.

[Prior Art] In recent years, aquaculture and cultivated fisheries have been rapidly promoted, but as these businesses expand, many problems are being clarified.

For example, in stationary fishing nets and aquaculture fishing nets that are dropped and deployed in the sea for a long period of time, a large amount of shellfish and algae adhere to the surface of the material over the course of use. There were problems such as poor growth of fish, death and death, and tidal current, loss of net due to wave resistance, damage, etc.

In order to prevent these drawbacks, a highly toxic anti-fouling agent for fishing nets, which is generally called “sea herbicide”, is applied to the net, for example, chemicals containing organic tin, copper, zinc, cadmium, mercury, etc. as main components. This was the main measure taken.

However, the use of such chemicals causes the formation of malformed fish, adversely affects humans due to the accumulation of chemicals inside the fish body, and further inhibits the normal growth of algae and shellfish in the surrounding clean sea area, It also induced the so-called Isoyaki phenomenon and prevented normal reproduction of seafood.

[Problems to be Solved by the Invention] In view of the above points, an object of the present invention is to produce an aquatic material that has excellent anti-adhesion properties against algae, shellfish, etc. and is pollution-free. It is intended to provide a way to do it.

[Means for Solving the Problems] The method for producing a marine product according to the present invention, which achieves the above-mentioned object, is a method of planting thinning-type composite fibers capable of generating fine fibers of 0.4 denier or less on the surface of a marine product material. After that, the method for producing an algae-proof marine product is characterized by subjecting to a fine treatment to 0.4 denier or less.

Further, in a preferred embodiment of the method for producing a marine product according to the present invention, the fibers to be transplanted are formed from those having crimps or latent crimping ability. It is a method of manufacturing a marine product for marine products.

[Operation] Hereinafter, the present invention will be described in detail.

It is said that algae and shellfish are unlikely to adhere to relatively soft ones, smooth ones with few surface irregularities, or those that easily shake.

The present inventors have studied how to artificially produce a material having such properties, and in particular, the shape of the substrate surface and the epiphytic condition with algae and shellfish spores, zoospores or larvae. In the process of studying, by coating the surface of the marine product material with napped fine fibers, epoch-making algae without coating or kneading chemicals with conventional biofouling preventive properties on these materials It was found that a shellfish-preventing effect can be obtained, especially on the surface of marine products.
An effective method is to implant a large number of fine fibers of 0.4 denier or less.

The flocking method that can be adopted in the method of the present invention typically includes an electrostatic flocking method (hereinafter referred to as electro-planting), a shake-off method, a tufting method, etc. The electro-planting method is the most preferable, and it is preferable to use the up-type electro-planting technique to lengthen the nap. Although it is possible to lengthen the naps by the shake-off method, the naps are coarse and inclined, and therefore the naps may be used properly depending on the fineness of the short cut fibers used, the hardness of the material, and the like.

From the viewpoint of the durability of the naps or the densification of the naps, the electro-planting technique is preferable.

In particular, since it is dropped into the sea for a long time, it is effective to enhance the durability of the napped hair. From this point, it is preferable to use a solvent-based resin, for example, a solvent-based urethane resin as the adhesive, but a non-solvent-based water-based adhesive. A resin, for example, an acrylic resin or a urethane resin may be used, and such an adhesive may be appropriately selected depending on the place where the marine product material of the present invention is used, the use conditions and the like.

Also, regarding the length of the naps that coat the surface of the marine product material, from various viewpoints such as economical efficiency, weight, and processability,
It is advantageous that the length is as short as possible within the range of having good anti-algae and shell-repellent effects. Therefore, a napped structure can be manufactured by using a napped knitted fabric which is generally processed or a napped yarn such as a chenille yarn. However, in these napped fabrics or napped yarn technology, a short nap length is adopted. In this case, there is a problem that the naps are very likely to fall off, and it is extremely effective to adopt the hair transplanting method, particularly the electro-planting method, as in the present invention.

When planting fine fibers, if the fibers are too thin, it is difficult to lengthen the naps due to processing technology.To enhance the algae proof effect, denier of the fine fibers that coat the surface of the final product should be used. Finer and longer naps, more micro voids are formed between fine fibers to improve water retention, tidal current,
From these points, it is preferable to use a thinnable composite fiber as the fiber to be planted, because it is preferable that the rocking action by waves is sufficiently performed and the surface is always slippery while having a slimy feel. It's good.

Here, the thinnable composite fiber is a composite fiber using a polymer of at least two components, and is divided or peeled by an appropriate thinning technique such as heat treatment, chemical treatment, physical treatment, Alternatively, it refers to a composite fiber in which at least one component is removed and which can be made into a fine fiber. For example, polymer array type fibers, chrysanthemum split type fibers,
Sea-island type blended fibers, multi-layered fibers and the like can be used, but not limited thereto.

In the method of the present invention, generally, as the fiber-forming polymer constituting the fine fibers, polyethylene terephthalate and its copolymers, polyesters such as polybutylene terephthalate and its copolymers, nylon 6, 1
Polyamides represented by 1, 12, 66, 610 and the like, copolymers thereof, acrylic polymers, polyurethane, polyethylene, ultra high molecular weight polyethylene, polypropylene and copolymers thereof, polystyrene and copolymers thereof Kind,
Any fiber type modified polymer such as polyvinyl alcohol, modified polyvinyl alcohols and rayon can be applied. These can be used alone or in the form of mixed fibers or composites.

The cross-sectional shape of the fiber is not particularly limited, and a circular shape, a modified shape, a hollow shape, a core-sheath shape, or the like is appropriately used.
As a method for obtaining these fine fibers, it can be easily produced by an appropriately selected single-component melt spinning technique or composite spinning technique.

As the thinning treatment after the flocking, it is preferable to perform heat treatment, solvent treatment, physical treatment, or the like to thin the hair.

When the material formed by the manufacturing method of the present invention is a rope-like material, a net-like material may be further processed using an appropriate net-making device to form a net-like material. At this time, the thinning treatment step may be performed at the stage of the rope-like material before net-making, or may be performed after net-working.

The hardness of the napped hair that coats the base material surface depends on the fiber denier and the material, and the property of transmitting the oscillating action due to tidal current and waves depends on the fiber nap length, denier and the hydrophilicity and hydrophobicity of the material. It depends. Also, how to make spores, zoospores, or larvae of algae, shellfish, etc. in the sea into a surface state that is difficult to settle, or how difficult to take root even if they settle, and how to drop them Moreover, how to combine such properties on the surface of marine products is an important point.

As a result of examination considering these points, the present inventors found that 0.4
It is important to transplant a large number of hairs using fibers having a denier or less, and if it exceeds 0.4 denier, the elasticity of the fibers becomes strong and the rocking action in seawater is reduced, and algae and shellfish are easily attached, which is not preferable.

Further, the fine fibers may have crimps. In that case, due to the crimped structure, seawater easily enters between the naps of the fine fibers,
In addition, the water retention is remarkably improved, the surface of the material is always slimy, and it is sensitive to the swaying action due to tidal currents and waves. Is preferable because it can easily be removed. Although the standing fibers of fine fibers of 0.4 denier or less have an effect of preventing the adhesion of algae and shellfish just by covering the surface of the net-like or rope-like material, in order to exert the effect of the present invention more strongly, It is preferable to elongate the napped length of the fine fibers covering the surface of the material. With regard to such napped length, the napped length as a guideline is 0.5 mm or more in consideration of economic efficiency, workability, place of use, size of effect, etc.
It is recommended to set it to 5 mm or less. If the nap hair length is less than 0.5 mm, the nap hair will not be able to transmit a sufficient rocking action due to the tidal current and wave resistance, and algae, shellfish spores, zoospores, or larvae are likely to attach, which is not preferable, while the nap hair length exceeds 45 mm. Therefore, there is a tendency that inconveniences such as difficulty in manufacturing technology and weight increase occur. If you want to increase the length of naps, use the up-planting method with an up-flowing ionic wind from the bottom, or the fluffing method if the napped density may drop slightly. Good to do.

Therefore, even if it is easy to process electro-planting, by adopting 0.4 denier or less and raising the nap density as much as possible, it is possible to obtain good swayability and slimy feel of the nap, and regarding the nap length. It can be said that it is better to use a relatively short one.

Short cut fibers are prepared by cutting these fine fibers to an arbitrary length. As described above, the cut length is preferably set such that the nap length is 0.5 mm or more at the final product stage. The short cut fibers are flocked on the surface of the marine product material.

The material of the marine product may be appropriately selected depending on the place of use, weight, hardness and softness, but the important point is the napped fine fibers coating the surface of these materials as described above. The material other than the portion forming the napped hair of the material may be the same as or different from the napped fiber, and is not particularly limited.

The fishery material of the present invention may be colored. Photosynthesis greatly influences the growth of algae. Germination of algae spores,
The growth of germination differs depending on the amount of light and the quality of light.There are many bright and red long-wavelength parts in a shallow place, and darker as it deepens, and only changes to green, blue, and purple parts, and different algae species inhabit. come. Therefore, it is possible to further enhance the effects of the present invention by making the color tone such that the spores of algae hardly adhere and grow as much as possible. From this point of view, the final coating color of the napped hair depends on the depth of use of the material or the species of algae that grows in the sea area where the material is used. It is preferable to select a coloring that does not easily absorb. Also,
The coloring method may be a method using pre-colored undyed fiber as the fine fiber, or a dyeing treatment of the finished material product.

The marine product material of the present invention is one obtained by adding an appropriate biofouling-preventing agent, kneading a material having a biofouling-preventing effect into the napped fiber itself, or enclosing it in fine particles such as microcapsules. It is also preferable to incorporate fine particles into a polymer and use fine fibers as napped fibers in order to more strongly exert the intended effect of the present invention.

As described above, according to the present invention, conventionally, in the field of marine product materials of this type, there was no technical idea of making the surface of the fibers fine fibers in order to prevent adhesion of algae, shellfish, etc., In this field, traditionally mainly in the field of clothing,
By applying fine fibers or ultrafine fibers used in the artificial leather field etc. as a material constituting material, a marine product having an epoch-making excellent effect in preventing adhesion of algae, shellfish, etc. is provided. It is a thing.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited or restricted by these Examples. Rather, it brings about the next application development.

Example 1 Polyethylene terephthalate was used as the island component and hot water-soluble polyethylene terephthalate was used as the sea component, and the component ratio (island component / sea component = 78/22% by weight) of 75D-18F composed of 16 islands A short cut fiber with a cut length of about 3.2 mm was prepared with a guillotine cutter by using a polymer mutual array type fiber yarn and converging it in a tow shape.

An adhesive of solvent-based urethane resin was applied to the surface of a commercially available fishing net (using black-dyed polyethylene terephthalate yarn, 210d / 20 × 3 combined yarn), and the above short cut fiber was electro-planted at an applied voltage of 20 kV. Then, it was immersed in hot water at 98 ° C. to perform a thinning treatment to remove sea components, and then dried with hot air.

The obtained net had a fiber denier of about 0.2 d, was napped, and was densely and satisfactorily covered with a nap of fine fibers of about 3 mm.
This net was cut into a width of 10 cm and a length of 50 cm, attached to a stainless steel frame, and dropped about 2 m in the sea.

The results of observing the state of attachment of algae and shellfish to the surface of the net after 1 month, 3 months, and 6 months of submersion in the sea are as shown in Table 1.

Example 2 Island component / sea component = polyethylene terephthalate / hot water soluble type polyethylene terephthalate, island / sea component ratio = 80
/ 20 wt%, polymer inter-array fiber with 16 islands,
Island component / sea component = isophthalic acid copolymerized polyethylene terephthalate / heat-soluble polyethylene terephthalate,
A 50/50% mixture of the island / sea component ratio = 80/20% by weight and a polymer mutual array type fiber with 16 islands was used in the spinning process 108
D-18F drawn filament yarn was prepared.

First, the filament yarn was bundled into a tow shape and cut into 4.2 mm with a guillotine cutter to make a short cut fiber.

Then, the commercially available fishing net used in Example 1 was used, and the plants were electro-planted under the same conditions. After that, a dry heat treatment was performed at 180 ° C. for 3 minutes, and then it was immersed in hot water at 98 ° C. to remove sea components and dried.

The net thus obtained was a net which was densely and well covered with naps of fine fibers having fine crimps with a nap length of about 4 mm and a fiber denier of about 0.4 d on the surface. This net was dropped into the sea in the same manner as in Example 1.

The results of observing the adhesion state of algae and shellfish on the surface of the net after being dropped in the sea are as shown in Table 1.

Comparative Example 1 Commercially available fishing net used in Example 1 (black, original PET, 210d / 20
X 3 yarns) were cut and dropped in the same manner as in Example 1. The results of observing the state of adhesion of algae and shellfish to the surface of the net after being dropped in the sea are as shown in Table 1.

As can be seen from these results, the nets coated with fine fiber naps produced by the method of the present invention exhibited superior anti-algae and armor effect compared to commercially available fishing nets.
In addition, the napped fibers that coat the surface of the net are ultrafine fibers that have long napped lengths and have crimps, and exhibited extremely excellent algae-proofing properties even after being dropped into the sea for a long time.

[Effects of the Invention] According to the present invention as described above, the secondary anti-adhesion property of algae and shellfish is remarkably excellent by a relatively simple method, which is a drawback of the similar conventional fishery material technology. An excellent material for marine products that can suppress the occurrence of specific pollution is provided.

Therefore, for a fixed net or aquaculture net of Thailand, yellowtail, tuna, flounder, etc., to be installed in the sea for a long time,
By using the material of the present invention, the effect of preventing malformation of fish, damage to the fish body, sediment contamination of the bait due to clogging of the net, and oxygen deficiency due to a decrease in tidal current, and improved workability, and economical It is also excellent.

In addition, by using it for ship mooring ropes, seafood, aquaculture ropes for algae culture, etc., it is possible to prevent shellfish and algae from adhering, improve workability, and prevent damage and runoff due to tidal currents and waves. .

Continuation of the front page (56) Reference JP 61-158506 (JP, A) JP 47-14462 (JP, A) JP 59-127750 (JP, A) JP 55-62265 (JP , A) Jitsuko Sho 53-39673 (JP, Y2) Jpn. Application No. 51-10385 (Jpn. Pat. Appln. No. 52-102824) A microfilm (JP , U) Practical application Sho 60-23794 (Actual development Sho 61-140824) Micro film (JP, U) Practical application Sho 51-14202 (JP, U) Micro-film (JP, U) of the contents and drawings attached to the application of Japanese Utility Model No. 52-105933)

Claims (2)

[Claims] 1. Flocking a thinnable composite fiber capable of generating fine fibers of 0.4 denier or less on the surface of a marine product material,
A method for producing an algae-proof aquatic material, which comprises subjecting the material to a fine treatment of 0.4 denier or less. 2. The method for producing an algae-proof aquatic material according to claim 1, wherein the flocking is performed by an electro-planting method.