JPH0129908B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a textile material for fisheries that has excellent performance and durability as an antifouling and algae-proofing net. Conventionally, various synthetic fibers have been used as textile materials for marine products and are produced in large quantities.However, when these synthetic fibers are used in the sea for a long period of time, they tend to cause damage to seaweed such as sea lettuce, shellfish such as barnacles, and seaweed. It is known that large amounts of marine animals, such as Therefore, various types of anti-fouling and anti-algae treatments are normally applied to textile materials that are used under the sea for long periods of time. Not only is it difficult to apply a sufficient amount of antifouling and algae treatment agent to textile materials with a small surface area, but also the antifouling and algae treatment agent may fall off due to friction and abrasion during use, or may be leached into the sea. There was a problem that it was fast and lacked durability. The present inventors have developed a monofilament marine fiber material having excellent antifouling and algae-proofing properties,
The present invention was developed through extensive research into fiber materials particularly useful as monofilament nets. That is, an object of the present invention is to provide a fiber material useful as a material for an antifouling and algae-proofing net with excellent durability. Such an object of the present invention is that the depth is at least
Approximately 4 or more recesses each having a depth of at least 10μ are formed in succession along the fiber axis direction.
A hydrophobic monofilament yarn having a fineness of 100 to 1500 denier (D), at least the surface of the monofilament is composed of a mixture of water-soluble polymers, and the entire monofilament is antifouling and algae-resistant. This can be achieved by resin processing using a resin composition containing the agent. The monofilament yarn of the present invention is made of polyamide,
It is made of a known hydrophobic fiber-forming polymer such as polyester or polyolefin, preferably polyamide, and the recesses (including cracks, hereinafter simply referred to as recesses) formed on the surface thereof have a depth of at least about 10 μm,
Preferably it needs to be 20μ to 300μ.
The depth of the recess on the surface of this monofilament is approximately 10μ
When the size is smaller, the adhesiveness of the processing agent decreases when antifouling and algae treatment is performed. Furthermore, the concave portion has a continuous shape along the fiber axis direction, and this continuous concave portion forms a further large number of concavo-convex portions and small holes by combining or twisting a plurality of monofilaments. Similarly, it is necessary that the monofilament surface has at least four continuous recesses, and if there are fewer than four, the effect of the antifouling and algae treatment will not be sufficient, which is not preferable. Furthermore, the fiber material of the present invention has a fineness of about 100 to
It is necessary to have a monofilament of 1500D, preferably 200-1000D, this range being related to the depth of the recess provided in its surface,
If it is smaller than 100D, the strength performance as a monofilament will be insufficient, while if it exceeds 1500D, flexibility will be lost, and it will be rigid and difficult to knit into net fabrics, handle, or work, which is not preferable. The present invention is characterized in that, in addition to such a monofilament, at least its surface is made of a mixture of water-soluble polymers. As described below, this water-soluble polymer is bonded to the antifouling and algae resin composition to improve adhesiveness. Therefore, the polymer must be present at least on the surface of the monofilament. The present invention has been able to provide a marine fiber material with excellent durability in antifouling and algae-proofing effects through the synergistic effect of the effect of the polymer and the effect of the monofilament. As described above, the marine fiber material of the present invention can be easily subjected to stain- and algae-proofing treatment and can be made into an excellent stain- and algae-proofing net fabric. That is, as an antifouling and algae-proofing net fabric, a net fabric is created by a known method using the marine fiber material of the present invention, and this net fabric is coated with, for example, triphenyltin hydroxide, tributyltin chloride, triphenyltin chloride, etc. organotin compounds such as tin fluoride;
Organotin polymer compounds such as tributyltin methacrylate copolymer, cuprous oxide, tetramethylthiuram disulfide, bis(2-pyridylthio-1-
oxide) Resins containing various antifouling and algae agents such as zinc, tetrachloroisophthalonitrile, cuprous thiocyanate, etc., such as rosin, acrylic resin,
Apply polyvinyl acetate, ethylene-vinyl acetate copolymer, etc. to the net fabric by impregnating or spraying it as an organic solvent solution or an aqueous emulsion dispersion, and then drying or heat-treating it to make it an antifouling and algae-proofing net fabric. Can be done. As mentioned above, the marine fiber material of the present invention is made of polyvinyl alcohol (PVA) and olefin copolymer.
PVA (modified PVA), polyvinyl polypyrrolidone,
A fiber-forming synthetic polymer mixed with a water-soluble polymer such as a water-soluble copolyamide or a water-soluble copolyester is disposed at least on its surface layer. Specific examples of such water-soluble polymers include polyethylene terephthalate and polyamide, which are copolymerized with water-soluble components such as polyalkylene glycol (eg, polyethylene glycol and tetramethylene glycol). Such a water-soluble polymer has excellent wetting properties with the above-mentioned stain-proofing and algae-proofing resin composition, and is characterized by exhibiting strong adhesion to such a composition. Also,
A large number of such water-soluble polymers are dispersed on the surface of the fibers, and a small amount of this water-soluble polymer is eluted with water, and fine irregularities are formed on the surface while the polymer remains. A fibrous material containing such a water-soluble polymer and having irregularities can greatly improve the retention of the antifouling and algae resin composition, and can also significantly improve the durability of this effect. The marine fiber material of the present invention has sufficient fiber strength, but preferably has a wet knot strength elongation (JIS, L-1070) of 3.5 g/d or more,
The polymer composition, fineness, depth of recesses or cracks, etc. are preferably selected within the range specified in the present invention so that the product of wet knot strength and wet knot elongation is at least 50 or more. Hereinafter, the textile material for marine products according to the present invention will be explained in more detail with reference to the drawings. FIG. 1 is a sectional view showing an example of the textile material for marine products of the present invention. In this figure, the surface of a monofilament 1 made of a fiber-forming polymer having four concave portions is coated with a layer made of a mixed polymer of the fiber-forming polymer and a water-soluble polymer 2, and The surface is resin-treated with antifouling and algae-proofing agent resin composition 3. The recess (crack) in FIG. 1 has a depth of more than 10 μm, and this recess exists continuously along the fiber axis. These recesses increase the surface area, the anchoring effect, and the probability of contact with the water-soluble polymer, thereby exerting a synergistic effect of improving the adhesiveness and durability of the antifouling and algae effect. In the present invention, it is important to have at least four such recesses. In other words, the recess is 0~
The above-mentioned effects of the present invention are small for the three monofilaments, and in the case of only monofilaments, even if the antifouling and algae resin composition is applied by resin processing, its falling off cannot be avoided, and the monofilaments of the present invention It is not desirable as such. In this way, the present invention selects a specific monofilament and pursues a synergistic effect between the water-soluble polymer present on its surface and the antifouling and algae resin composition by increasing the contact probability between them. This is what I did. FIG. 2 shows a cross section of an example of the monofilament of the present invention. In this example, the apex of the convexity
There are 6 recesses continuous in the fiber axis direction with a distance of approximately 10 μ or more from the deepest part Y ₂ corresponding to the midpoint Y ₁ between X ₁ and the apex X ₂ of the projection adjacent to this projection. It is formed. The depth of this recess greatly contributes to the bondability with the water-soluble polymer and furthermore the bondability with the antifouling and algae resin composition, and the deeper the recess, the higher the bondability. In the monofilament shown in Figure 2,
The entire fiber may be formed by melt-spinning a mixture of a fiber-forming polymer and a water-soluble polymer, or the core portion may be formed only of the fiber-forming polymer, and the above-mentioned mixture may be formed on the surface of the fiber. A layer made of a polymer may be formed. In either case, the effects of the present invention can be fully achieved by resin processing with the antifouling and algaecide resin composition. FIG. 3 is a schematic diagram of a twisted yarn consisting of a plurality of resin-treated monofilaments as a textile material for marine products according to the present invention. As can be seen from this figure, the twisted yarn of the present invention has countless microscopic spaces that communicate with the outside, which improves the adhesion of the antifouling and algaecide resin composition, and further reduces knots in the net fabric. It exhibits characteristics such as excellent properties such as strength. Hereinafter, the present invention will be explained in more detail with reference to Examples. Examples 1-2 and Comparative Examples 1-2 Polyethylene terephthalate (IV
= 0.8) at a spinning temperature of 290°C, and the spun yarn was cooled through a cooling bath with a water temperature of 40°C, immediately passed through a heating water bath with a water temperature of 90°C, stretched 4.3 times, and wound up. In this case, as shown in FIG. 1, the first level was a composite of a core-sheath type polymer in which a water-soluble polymer was mixed with polyester. For other items, the indicated caps were used. These threads were passed through a xylene solution of tributyltin methacrylate to give a coverage of 14%. These raw yarns were combined and twisted into a twine of approximately 18,000 denier. A net with a mesh size of 100 mm was knitted using this twine. These nets were immersed in the sea and the status of adhesion of seaweed, shellfish, and marine animals was observed.As a result, the net shown in Figure 1 of the present invention had almost no adhesion even after 6 months of being immersed in the sea. Furthermore, the condition did not change even after 10 months, indicating that it had excellent antifouling and algae-proofing properties as well as its durability. However, when the antifouling and algae resin composition was applied directly to polyester monofilaments of various cross sections, some of them were effective for up to 6 months, but others were leached and lost their effectiveness after 3 months. Disappeared. That is, in the case of the round cross-section one, the resin composition was intermittently peeled off considerably during the twisting process and the knitting process, and the dissolution rate was high, and seaweed grew after 3 months (Comparative Example 1). In addition, some parts of the cocoon-shaped cross section peeled off during the knitting process, and after 3 months of soaking, they eluted.
Seaweed started to grow after 4 months (Comparative Example 2). Next, the one with a star-shaped cross section had an antifouling and algae effect for up to 6 months, but after that it eluted, and after 8 months, shellfish and seaweed were attached (Comparative Example 3). Furthermore, after 10 months, seaweed and shellfish had grown in all of the comparative examples.

[Table] × mark: No effect △ mark: Small effect ○ mark: Effective ◎ mark: Particularly effective

[Brief explanation of drawings]

FIG. 1 is a sectional view of a water-soluble polymer-containing monofilament having an antifouling and algaecide resin composition layer of the present invention on its surface, and FIG. 2 is an example of the monofilament (core) applied to the present invention. FIG. 3 is a schematic diagram of a twisted yarn made of a plurality of resin-treated monofilaments as a textile material for marine products of the present invention. In the figure, 1: monofilament of fiber-forming polymer, 2: water-soluble polymer, 3: antifouling and algaecide resin composition.

Claims (1)

[Claims] 1 Approximately 100 concavities with a depth of at least approximately 10μ are formed in four or more consecutively along the fiber axis direction.
A hydrophobic monofilament yarn having a fineness of ~1500 denier, at least the surface of the monofilament is composed of a mixture of water-soluble polymers, and the entire monofilament is blended with an antifouling and algae agent. A textile material for marine products characterized by being resin-processed using a resin composition.