JPH0482113B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to fishery materials with excellent biofouling prevention properties. [Background Art] In recent years, aquaculture and cultivation fishing in coastal waters have been rapidly promoted. As these projects expand, many problems are becoming apparent.
For example, with fiber materials used for aquaculture and cultivation, a large amount of seaweed or shellfish may adhere to the surface of the materials while they are being dropped into the sea, resulting in a decrease in work efficiency, damage to the materials by currents and waves, and loss of the materials. The following problems have occurred. In order to solve these problems, the following methods have been proposed. That is, JP-A-59-14738 describes a method for applying copper plating to the surface of textile materials;
Publication No. 35735 discloses a method of coating the surface of a fiber material with a water-swellable polymeric substance, and JP-A-58-201862 discloses a method of coating the surface of a fiber material by mixing a water-absorbing elastomer and copper (alloy) powder. , Japanese Patent Publication No. 1973
-79024 describes a method of coating textile materials with diethanolamine derivatives,
Publication No. 157824 discloses a method of coating fiber materials with organic tin compounds, zinc oxide, etc. These conventional techniques are expected to have a certain degree of effectiveness in improving the above-mentioned problems from the viewpoint of preventing the adhesion of algae and shellfish to the surface of fiber materials. However, the chemicals used in these conventional techniques have considerable toxicity to the human body. In addition, if these chemically treated products are dropped into the sea, they will also inhibit the adhesion of algae and shellfish in the surrounding clean waters, inducing the so-called Isoyaki phenomenon, and also hindering the normal reproduction of fish and shellfish. It was hot. These chemicals are toxic and are commonly referred to as "marine herbicides," and there is a strong need to establish production technology that does not require reliance on such toxic chemicals and to improve aquaculture management technology. This is what is currently required. [Problems to be Solved by the Invention] In view of the above-mentioned points, an object of the present invention is to have the effect of effectively preventing the adhesion of algae and shellfish, and to substantially eliminate the problem of secondary pollution. The aim is to provide materials for fisheries. [Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, the present inventors have finally arrived at the fishery materials of the present invention that are excellent in preventing biofouling. That is, the fishery material of the present invention is a fishery material with excellent biofouling prevention properties, and is characterized by being covered with raised fluff consisting mainly of crimped fine fibers of 5 deniers or less. [Function] Hereinafter, the present invention will be explained in detail. Conventionally, with regard to this type of textile material for marine products, as long as it maintained practical strength, the textile material itself was not considered very important, and the main emphasis was placed on the chemicals used to coat the base material. This had the problem of secondary pollution. On the other hand, algae and shellfish in the sea are said to have difficulty adhering to relatively soft objects, smooth objects with little surface irregularities, or objects that are easily shaken. The present inventors researched how to artificially create materials with such properties, and in particular, investigated the shape of the substrate surface and the adhesion status of spores, zoospores, and larvae of algae and shellfish. In the process of investigation, we discovered that by coating the surface of the base material mainly with napped fine fibers with crimps, we could create an innovative solution without having to coat or knead conventional chemicals with biofouling prevention properties onto the fiber surface. It was discovered that this effect can be obtained. In other words, the hardness and softness of the nap that covers the surface of the base material depends on the fiber denier and the material, and its ability to transmit the oscillating motion caused by tides and waves is
It depends on the nap length and denier of the fiber, and the hydrophilicity and hydrophobicity of the material. In addition, how to make the surface conditions difficult for spores, zoospores, or larvae of algae, shellfish, etc. to attach to the surface of the sea, and even if they do attach, how to make it difficult for them to take root, and how to make them fall off. The important point is how to combine and realize such properties on the surface of the base material. As a result of studies taking these points into consideration, the marine products material of the present invention is covered with a large number of raised fluffs made of fine fibers of 5 denier or less, preferably 1.5 denier or less, and most preferably 1 denier or less. It is. If it exceeds 5 denier, the stiffness of the fibers will become strong and the rocking action in seawater will be reduced, and the surface will become uneven, making it easy for algae and shellfish to adhere to it, which is undesirable. A further important point in the present invention is that the aforementioned fine fibers have crimps. Because it has crimps, it is easy for seawater to enter between the fine fibers, and its water retention is significantly improved.
It always gives a slimy feel to the surface of the material and is sensitive to the shaking action of tides and waves, making it difficult for spores, zoospores, or larvae of algae and shellfish to attach, and even if they do attach, they fall off easily. . Performance such as sliminess and water retention can be achieved by making the napped fibers themselves hydrophilic, but by making the napped fibers ultra-fine and crimped, the napped material has hydrophilic and hydrophobic properties. It is advantageous to make it even better regardless of its properties. Common methods for generating crimp include, for example, a crimp mix that utilizes the difference in shrinkage of polymers, crimp generated by false twisting, or mechanical crimp application using a crimper. However, it is not particularly limited. The shape of the crimp is not only a two-dimensional crimp that is simply bent in the length direction, but also a three-dimensional crimp that is spiral or loop-shaped and bent in the length direction, or a mixture of these. Good too. The number of crimps differs depending on the length of the pilaster and should not be uniquely limited, but when shortening the pilaf length, it is better to add more crimps for better water retention and a longer pilaf length. In some cases, it may be smaller. What is important is that it has good water retention properties and is easily swayed by the resistance of waves and currents. As a guideline for the number of crimps to provide such performance, it is preferable to set the number of crimps to 2/(pilp length) or more. In the present invention, "raised hair consisting mainly of fine fibers with crimps..." means that fine fibers without crimps may be mixed in a moderate amount as long as the effect of the present invention is not impaired. do. Although the nap of the fine fibers having crimps can have the effect of preventing the adhesion of algae and shellfish just by covering the surface of the base material, in order to bring out the effects of the present invention even more, the length of the nap of the fine fiber must be adjusted. It is preferable to make it long. Regarding the nap length, considering economic efficiency, workability, place of use, size of effect, etc., it is recommended that the nap length should be 0.5 mm or more and 45 mm or less. When the piloerection length is less than 0.5 mm, the piloerection becomes a trend.
Due to wave resistance, sufficient rocking motion is not transmitted, making it easier for algae, shellfish spores, zoospores, and larvae to attach. On the other hand, if the nap length exceeds 45 mm, various inconveniences will occur, such as difficult manufacturing techniques and increased weight. Therefore, the nape fibers are on the thin side.
It is preferable to use 1.5 denier or less, or even 1 denier or less, and make the nap length relatively short. For example, if the napped fiber is less than 1 denier, it is best to set it to about 0.5 to 20 mm.
In addition, in the case of 1 to 3 denier, it is about 0.5 to 30 mm,
Furthermore, in the case of slightly thicker 3 to 5 deniers, 0.5
It is best to set it to ~45mm. In addition, the appropriate range of the nap density of the nap fibers varies depending on the combination of the nap length and fiber denier, but when the form of the marine material is a fabric or a thick rope, In the case of thin rope-like materials or net-like materials, the number should be approximately 4,000 to 6,000,000 fibers/ ^cm2 , and in the case of thin rope-like materials or net-like materials, the number should be approximately 4,000 to several 100,000 fibers/cm2 to reduce the slimy effect, unevenness, and Although it is preferable in consideration of the fluctuating nature of the nap, etc., it goes without saying that materials outside the above-mentioned range may be employed as long as the intended effects of the present invention are not impaired. In general, from the viewpoint of ease of forming fine fibers, 10,000 to several
The most practical range is approximately 100,000 lines/cm ² . When using ultra-fine fibers such as 0.001 denier or less, the upper limit is 5 million to 600 as shown above.
It is quite possible to form ultra-high-density raised hairs of around 10,000 hairs/cm ² , but if we take into account the ease of production, it is actually possible to form up to about 100,000 hairs/cm ² as mentioned above. It can be said to be a target. Polymers forming the fine fibers used in the present invention include polyesters such as polyethylene terephthalate and its copolymers, polybutylene terephthalate and its copolymers, nylon 6, 11,
Polyamides represented by 12, 66, 610, etc. and their copolymers, acrylic polymers, polyurethane, polyethylene, ultra-high molecular weight polyethylene,
Any fiber-forming polymers such as polypropylene and its copolymers, polystyrene and its copolymers, polyvinyl alcohol, modified polyvinyl alcohol, and rayon can be applied, and fine fibers made of these polymers may be used alone or It is used as a mixed fiber or mixture. The cross-sectional shape of the fine fibers is not particularly limited, and shapes such as circular, deformed, hollow, core-sheath, etc. are used as appropriate. The marine materials of the present invention may be colored.
The growth of algae is largely determined by photosynthesis. The germination of algae spores and the growth of germinated bodies vary depending on the amount and quality of light. In shallow areas, there are many bright red and long-wavelength parts, and as you get deeper, the light becomes darker and changes to only green, blue, and purple parts. The types of algae that live there also vary. Therefore, the effect of the present invention is further enhanced by a color tone that makes it difficult for algae spores to adhere and grow. From this point of view, the color tone of the final material itself and the standing floes should be determined depending on the type of algae growing epiphytically in the sea area where the material is used, so that it is difficult for those algae to absorb light in the wavelength range suitable for photosynthesis. It is preferable to choose coloring. The fishery materials of the present invention can be used in the form of ropes, cords, fabrics, etc., as appropriate. For example, when making a rope shape, the surface of the twisted yarn is
The rope-shaped fishery material of the present invention, which is excellent in the bioadhesion prevention effect, can be obtained by flocking fine fibers of denier or less onto the surface of the rope. In addition, in this case, especially for flocking of ultra-fine fibers of 1.5 denier or less,
In general, the finer the fiber, the more difficult it is to process, so we usually cut and flock fibers obtained using composite melt-spinning and drawing techniques such as polymer mutual array fibers, sea-island blend fibers, and split fibers. Thereafter, by making the fibers ultra-fine using an appropriate ultra-fine technique depending on the fibers, a rope covered with ultra-fine fiber napped can be obtained. Moreover, if a net-like shape is desired, it can be easily obtained by processing the above-mentioned rope into a net by passing it through an appropriate net-making machine. In addition to the above-mentioned forms, the fishery materials of the present invention also include:
For example, the surface of a base material made of any material such as styrofoam, urethane foam, PVC sheet, cement, metal, ceramic, wood, etc. is covered with napped fine fibers having crimps that meet the conditions of the present invention. There are no particular limitations on its form or shape as long as it is. Furthermore, the base material or the fibers forming the nap used in the fishery materials of the present invention may be coated with or kneaded with a commonly used substance that has a biofouling prevention effect, or may be coated with or kneaded with a commonly used substance having a biofouling prevention effect, or may be a material such as microcapsules. The substance may be encapsulated in fine particles that are made into fibers or a base material, and such special fine fibers or base materials may be used. It is also effective to form the marine products material of the present invention by using it to enhance the intended effects of the present invention. As described above, in the field of this type of fishery materials, there has been no technical application idea such as making the surface of the material crimped with fine fibers to prevent attachment of algae, shellfish, etc. In Although,
In this field, by applying crimped fine fibers or ultrafine fibers, which have traditionally been used in the clothing field, artificial leather field, etc., as material constituent materials, we have improved the ability to prevent the adhesion of algae and shellfish. Fisheries materials with excellent long-term effects are provided. [Example] The present invention will be explained in detail below with reference to Examples.
The present invention is not restricted or limited by these Examples. Rather, it brings about the next application development. Examples 1 and 2 Island component/sea component = polyethylene terephthalate/polystyrene, island/sea component ratio = 80/20% by weight, 16 island fibers in mutually arranged polymers and island component/sea component = copolymerized polyethylene terephthalate / polystyrene, island/sea component ratio = 80/20% by weight, 16 island fibers with polymeric mutually arranged fibers.
81 denier (D) blended in a 50/50% spinning process
A drawn filament yarn of 18 filaments (F) was prepared. The island component fineness of this filament was 0.23d. First, the filament was cut into pieces of 2.7 mm (Example 1) and 5.3 mm (Example 2) using a guillotine cutter. Next, the above-mentioned cut fibers were electroplanted separately under the same conditions using a non-solvent adhesive on the surface of a commercially available fish culture net (black, spun-dyed PET210d/20 x 3 yarns). Next, the net was treated with dry heat at 180° C. for 5 minutes, and then immersed in trichlorethylene to remove sea components and become fine, and then dried. Each of the obtained nets has a surface with fine crimps, a nap length of about 2 mm, a number of crimps of about 2 mounds/(pile length), and a nap length of about 4 mm, a number of crimps of about 4 mounds/(pile length).
It was covered with raised microfibers. This net was cut into pieces of 10 cm wide and 50 cm long. This net was attached to a stainless steel frame and dropped into the sea approximately 2 meters. Table 1 shows the results of observing the state of adhesion of algae and shellfish to the net surface one month, four months, and nine months after being dropped into the sea. Example 3 75D- made of polyethylene terephthalate
Three 25F filaments were spun together and crimped by false twisting and crimping and reheat setting. This false twisted crimped yarn was bundled into a tow shape, and then cut with a guillotine cutter to a length of 2 mm. Next, the cut pile was electroplanted onto the surface of a commercially available fish net using a non-solvent adhesive. The obtained net had a surface covered with crimped naps with a nap length of about 2 mm. This net is used in Example 1.
It was attached to a frame similar to 2 and dropped into the sea. Table 1 shows the results of observing the adhesion of algae and shellfish to the surface of the net one month, four months, and nine months after dropping it into the sea. Comparative Example 1 Using the same filament yarn as Examples 1 and 2,
A cut pile of mm was created. Next, electroplating was carried out under the same conditions on the surface of the same commercially available fish net used in Examples 1 and 2. Thereafter, it was immersed in trichlorethylene to remove sea components and become fine, and then air-dried.
The net surface was covered with non-crimped, ultrafine fibers having a nap length of about 2 mm. This net was cut to a width of 10 cm and a length of 50 cm, attached to the same stainless steel frame as in Examples 1 and 2, and dropped and set into the sea approximately 2 m. Table 1 shows the results of observing the adhesion of algae and shellfish to the net surface one month, four months, and nine months after being dropped into the sea. Comparative Example 2 The filament yarn of 81D-18F polymer mutually arranged fiber used in Examples 1 and 2 was cut to a length of 3 mm using a guillotine cutter.
Next, the cut pile was electroplanted onto the surface of a commercially available fish net using a non-solvent adhesive. The net surface was covered with non-crimped naps having a nap length of about 3 mm, consisting of polystyrene as a sea component and polyethylene terephthalate as an island component. This net was attached to the same frame as in Examples 1 and 2 and dropped into the sea. Table 1 shows the results of observing the adhesion of algae and shellfish to the net surface one month, four months, and nine months after being dropped into the sea. Comparative Example 3 The commercially available fishing net used in Examples 1 and 2 was 10 cm wide.
It was cut to a length of 50 cm, attached to the same stainless steel frame as in Examples 1 and 2, and dropped and installed approximately 2 m into the sea. Table 1 shows the results of observing the adhesion of algae and shellfish to the net surface one month, four months, and nine months after being dropped into the sea.

【table】

[Table] As can be seen from these results, a large number of barnacles, young shellfish such as oysters, and sea lettuce were attached to the commercially available fishing net just one month after it was dropped into the sea, and an even larger amount was observed after 4 months. . On the other hand, those simply covered with raised non-crimped fine fibers,
Compared to commercially available fish nets, the effect of preventing the adhesion of algae and shellfish has been confirmed, but the product of the present invention, which is coated with crimped fine fibers, has even more excellent anti-algae and shellfish properties. It is effective. In particular, ultrafine fibers with crimps and long naps exhibited excellent effects even when dropped into the sea for long periods of time. [Effects of the Invention] The marine materials according to the present invention suppress the occurrence of secondary pollution, which was a drawback of conventional marine materials technology,
Moreover, it has excellent properties for preventing adhesion of algae and shellfish. Therefore, by using fixed nets that are left in the sea for a long period of time or aquaculture nets for sea bream, yellowtail, tuna, flounder, etc., it is possible to prevent the occurrence of deformed fish.
It is effective in preventing damage to fish bodies, contamination of bait due to clogging of nets, and oxygen deficiency due to decreased tidal currents, preventing the death of fish and shellfish, and improving workability.
It is highly economical. In addition, by using the rope for mooring ships, seafood, and algae cultivation, it is possible to improve workability and prevent damage and washout caused by currents and waves. Furthermore, by attaching it to the belly of a ship, the seawater inlet, the inner wall of a pipe, the surface of a navigational navigation buoy or a position indicating buoy, the surface of a support frame of an offshore platform, etc.
It is possible to effectively prevent the adhesion of organisms,
With these materials, the cost of repairs that would otherwise be required due to biofouling can be significantly reduced.

Claims (1)

[Scope of Claims] 1. A fishery material with excellent biofouling prevention properties, characterized by being covered with raised fluff consisting mainly of crimped fine fibers of 15 deniers or less. 2. A fishery material with excellent biofouling prevention properties as set forth in claim 1, wherein the fine fibers are ultrafine fibers of 1.5 denier or less.