JPH0681214A - Fiber having preventing effect on adhesion of aquatic life and fiber product - Google Patents

Abstract

PURPOSE:To obtain the subject yarn useful for finishing nets, etc., free from adhesion of aquatic lives, having non-toxicity to human body, excellent durability, comprising a resin composed of a polymer having a specific viscosity, a specific angle of water slippage and solubility and an antifouling agent, having a contact angle of water on the surface of a specific value. CONSTITUTION:A thermoplastic resin such as polyethylene terephthalate is blended with 0.1-60wt.% polymer (e.g. dimethylpolysiloxane) having >=1,000 centistoke viscosity at 25 deg.C and an angle of water slippage of <=12 degree and satisfying the formula (ASP is solubility parameter value of polymer; BSP is solubility parameter value of thermoplastic resin) and 0.01-60wt.% antifouling agent (e.g. copper dimethyldithiocarbamate), kneaded by a static mixer, extruded from a round hole nozzle having 295 deg.C spinneret temperature and 1,00m/minute take-off speed and drawn by a roller plate method by hot rollers at 79 deg.C and a hot plate at 150 deg.C to give the objective yarn having a contact angle of water on the yarn surface of >=90 degrees, having excellent durability, smooth surface, flexibility and processability free from emulsion and removal of the contained materials.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber having very little attachment of aquatic organisms when used in contact with seawater or fresh water for a long time, and a fiber product containing the fiber.

[0002]

2. Description of the Related Art Textile products used for a long period of time in seawater or freshwater include, for example, fixed nets for fisheries, fishnet products for fisheries, such as fishnets; mooring buoys, light buoys and buoys. Rope used: There is a pollution prevention fiber membrane used for civil engineering. These textiles, while being in contact with seawater or freshwater for a long period of time, have various aquatic organisms on the surface thereof, such as algae such as Ulva and diatoms, coelenterates such as sea anemones, sponges such as sea spiders, and the sea urchins. Annelids, tactile objects such as bryozoans, arthropods such as barnacles, protozoa such as ascidians, and molluscs such as mussels attach and live.

Due to the attachment of these aquatic organisms, for example, in the case of stationary nets, the nets sink due to an increase in weight, the nets are washed away due to an increase in water flow resistance, and the nets are damaged due to contact and bending.
Problems such as damage to the caught seafood have occurred. In addition, in the case of a net for net life, in addition to the net subsidence due to an increase in weight, oxygen deficiency due to a decrease in the fluidity of seawater or fresh water, and other major obstacles such as damage to livestock and seafood by various aquatic organisms will occur.

As a measure for preventing the adhesion of aquatic organisms to the textile products used in contact with sea water or fresh water for a long time,
Heretofore, a method of treating a textile with an organic tin compound such as tributyltin oxide, triphenyltin oxide, triphenyltin acetate, triphenyltin chloride, etc. has been widely adopted. However, the use of the organic tin compound has a problem that it causes a bad unpleasant odor or an irritating odor when processing a textile product, which deteriorates the working environment. Moreover, the abnormal accumulation of organotin compounds in the body of fish and shellfish leads to serious disorders such as malformation and death of fish and shellfish, and when humans ingest such seafood, they have a great adverse effect on the human body. It has been revealed in recent years that Therefore, the use of textile products treated with organotin compounds has come to be voluntarily restricted and tends to be totally prohibited.

Therefore, as one of the techniques which can replace the organotin compound having the above-mentioned great adverse effects, metals such as copper, silver, zinc and nickel, which have an adhesion inhibiting effect on aquatic organisms, and their compounds, Or nitrogen-based, sulfur-based,
There is a method of using an organic compound such as a halogen type. As a means for imparting these to a textile product, there is a method in which the powder thereof is mixed with a coating material made of a natural resin, a synthetic resin or the like, which is coated on the surface of the fiber and then cured. However, in this method, since the fibers become hard, the workability of twisting, warping, weaving, netting, etc. and the workability during use are poor,
Further, the roughness of the surface causes inconvenience such as damaging livestock fish and shellfish. Further, due to abrasion and the like, the active ingredient and the coating film fall off in a relatively short period of time, and the effect of preventing the adhesion of aquatic organisms disappears.

There is also a method of incorporating powders of metals, compounds thereof, or organic compounds having an adhesion inhibiting effect into the inside of the synthetic fiber, but when the amount of the compound is sufficient, spinnability and In terms of processability such as stretchability, strength of the fiber, and durability, what can be put to practical use cannot be obtained, and further, only the active ingredient present in the surface layer of the fiber contributes to the effect, so that after a short period of time, Then, the effect of preventing the attachment of aquatic organisms disappears.

Further, a method has been proposed in which a synthetic fiber, for example, a polyester monofilament contains polysiloxane (Japanese Patent Laid-Open No. 60-81312), but such a method has an effect of preventing adhesion of aquatic organisms. However, it has a drawback that its effect does not last for a long time.

As described above, the fact is that fibers which have a high effect of preventing adhesion of aquatic organisms, are durable, and can be put to practical use in terms of strength, processability, workability, etc. have not been obtained until now. .

[0009]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a fiber which is highly safe to fish and shellfish and human body, has durability, and can prevent adhesion of aquatic organisms for a long time, and a fiber product containing the fiber. To provide. Another object of the present invention is to provide a fiber for preventing adhesion of aquatic organisms and a fiber product containing the fiber product, which does not coarsen or harden the fiber product and does not damage the seafood caught or raised. . Further, an object of the present invention is to provide a fiber used for a fiber product such as a net or a rope, which has good workability such as twisted yarn, warp, weaving and netting, and has good workability during use, and a fiber product containing the same. Is also intended.

[0010]

Means for Solving the Problems As a result of research to solve the above problems, the present invention comprises a thermoplastic resin containing a polymer satisfying a specific condition,
The present inventors have found that fibers having a specific contact angle have an effect of preventing the adhesion of aquatic organisms, and that the effect can be maintained for a long period of time, leading to the present invention.

That is, according to the present invention, as a marine material, particularly a fiber product for fishery, 0.1 to 60% by weight of a polymer satisfying the following conditions (I) to (III), and 0 of an antifouling agent are used. It is characterized by preventing adhesion of aquatic organisms by using a fiber made of a thermoplastic resin containing 0.01 to 60% by weight and having a water contact angle of 90 degrees or more on the fiber surface. . (I) Viscosity at 25 ° C is 1000 centistokes or more (II) Water slip angle is 12 degrees or less (III)

[Equation 2]

It is preferable to use an organic polysiloxane as the polymer in the present invention, and various organic silicon compounds can be used as the organic polysiloxane, but those which are less likely to volatilize at the spinning temperature of the thermoplastic resin are preferred. is there. Particularly, the one having a weight loss rate of 1% or less when heat-treated at 150 ° C. for 24 hours is preferable. Specific examples include dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, etc., or 2
A mixture of two or more species can be used.

The viscosity of the above polymer is 1000 at 25 ° C.
It is not less than centistokes, preferably not less than 5000 centistokes. When the viscosity is less than 1000 centistokes, the durability of the effect of the present invention decreases. This is because, for example, when an organic polysiloxane is used as a polymer, if the viscosity is too low, migration of the organic polysiloxane in the fiber is likely to occur, and the organic polysiloxane that migrates to the fiber surface in seawater or fresh water is more likely than the fiber. It is presumed that it is easy to escape and the concentration of the organic polysiloxane in the fiber or on the surface of the fiber decreases. Further, when the viscosity of the organic polysiloxane becomes low, phase separation with the thermoplastic resin progresses, and not only the spinnability and stretchability are significantly lowered, but also the organic polysiloxane in the thermoplastic resin is used in the process of manufacturing a fiber product. It receives heat history and migrates to the fiber surface, resulting in poor texture of the fiber product.

Further, it is necessary that the sliding angle of water in the polymer is 12 degrees or less. When the sliding angle of water in the polymer exceeds 12 degrees, the effect of preventing adhesion of aquatic organisms to fibers and fiber products made of a thermoplastic resin containing the polymer is extremely reduced. In the present invention, it is preferable to use a polymer having a sliding angle of water in the range of 8 to 10 degrees. Furthermore, it is important that the following relational expression is established between the solubility parameter of the polymer (hereinafter abbreviated as SP value) and the SP value of the thermoplastic resin as the base material.

[0015]

[Equation 3]

If the SP value of the polymer and the SP value of the thermoplastic resin do not satisfy the above relational expression, the effect of preventing adhesion of aquatic organisms on the fibers and fiber products of the present invention is extremely reduced. That is, in the present invention, it is necessary that the polymer and the thermoplastic resin as the base material are appropriately dispersed.

Since the above-mentioned polymers represented by organic polysiloxanes (hereinafter, polymers are represented by organopolysiloxanes) are difficult to be compatible with a thermoplastic resin, a cross section perpendicular to the longitudinal direction of the fiber is obtained. (Hereafter abbreviated as fiber section)
In, it is dispersed in the thermoplastic resin in an island state. In the present invention, it is presumed that the antifouling agent, which will be described later, is gradually released to the fiber surface through the organic polysiloxane as a passage, so that the above effect is exhibited. Therefore, in order to smoothly carry out this sustained release, it is necessary to have a communication path connecting the islands of the organic polysiloxane in the fiber cross section to some extent, and for that purpose, the addition amount of the organic polysiloxane is 0. 1-6
0 wt% is required. When the amount added is less than 0.1% by weight, the number of islands made of organopolysiloxane in the fiber cross section and the communication paths between the islands are extremely reduced, and the sustained release property of the antifouling agent on the fiber surface is significantly reduced. On the other hand, if the amount added exceeds 60% by weight, filter clogging in the melt spinning process and yarn breakage due to fluffing are likely to occur. It is preferably 1 to 50% by weight. In particular, in the case of a resin-coated yarn obtained by coating a thermoplastic resin containing the above-mentioned polymer and an antifouling agent on a core yarn made of a thermoplastic resin as described below, 10 to 60 parts by weight of the polymer is used. % Can be contained in a large amount.

Examples of the antifouling agent of the present invention include metals having an effect of inhibiting aquatic organisms, powders thereof, alloys thereof, compounds thereof, and organic compounds having such an effect. Copper, silver, zinc, tin, nickel, etc. can be mentioned as said metal. Examples of the metal compound include oxides, halides, sulfides, and various salts of these metals. Examples of the organic compound include 2,4,5,6-tetrachloroisophthalonitrile, copper dimethyldithiocarbamate, and the like. Zinc dimethyldithiocarbamate, N-fluorodichloromethylthiophthalimide, N, N-dimethyl-N'-phenyl-
N'-fluorodichloromethylthiosulfamide, dichlorophenyldimethylurea, bis-2-pyridylthio-1-oxide zinc, 2,4-thiazolyl-benzimidazole, 2-n-octyl-4-isothiazoline-3
-One, N- (2 ', 6'-diethylphenyl) 2,3
-Dichloromaleimide, 4-chlorophenyl-3-yo-
Examples include dopropargyl formal and diiodomethyl-p-trisulfone. These metals, metal compounds, or organic compounds can be used alone or in combination of two or more kinds. Of these, metals, metal compounds, organic halogen compounds, organic nitrogen-sulfur compounds, and combinations thereof are preferable because they can remove all organisms (animals, plants, microorganisms, etc.). When using a metal, an alloy thereof, or a compound thereof as an antifouling agent, the average particle size thereof is 5 μm or less, particularly 1 μm or less,
A filter during melt spinning is preferred because it is less likely to cause clogging, fluff, and yarn breakage.

The amount of antifouling agent added to the fiber is 0.01 to 60.
% By weight, preferably 0.1 to 50% by weight, in particular 1 to 30
% By weight. Only a very small amount of antifouling agent contained in the fiber has an effect of preventing the adhesion of aquatic organisms, but in order to maintain the effect of preventing adhesion of aquatic organisms for several months or more, which is practically necessary, 0.1 It is necessary to add more than wt%. Further, if the amount of the antifouling agent added to the fibers exceeds 60% by weight, filter clogging or fluff yarn breakage easily occurs during melt spinning, and the obtained fibers also become hard and it is difficult to make a net or rope.

The thermoplastic resin of the present invention includes polyesters such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, nylon 12
Polyamide, etc .; Polyolefin, such as polyethylene and polypropylene; Polyurethane; Polyacrylate; Fluorine compounds such as polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride, tetrachloroethylene; polyvinyl alcohol; ethylene-vinyl alcohol copolymer And the like, and may be a mixture of two or more kinds, or a copolymer. Further, these resins may contain additives such as a fluorescent whitening agent, a conductivity improver, a modifier such as an ultraviolet absorber, a coloring pigment, a stabilizer and a flame retardant.

The cross-sectional shape of the fiber of the present invention may be any shape, and may be circular or irregular. In the case of an irregular cross section, for example, an arbitrary shape such as a flat shape, an elliptical shape, a polygon such as a triangle to an octagon, a T-shape, and a multilobal shape such as a 3 to 8 lobes can be used.

Further, the fiber of the present invention may have a form in which two or more kinds of thermoplastic resins including an organic polysiloxane and a thermoplastic resin to which an antifouling agent is added are compounded. The form of the composite fiber can be any form such as a core-sheath type, a sea-island type, a laminating type, and a mixed type thereof. In the case of the core-sheath type, either a two-layer core-sheath type or a multilayer core-sheath type having three or more layers may be used. In the case of the sea-island type, the shape, number and dispersion state of islands can be arbitrarily selected. In the case of the bonding type, the bonding surface in the cross section of the fiber may be in a linear shape, an arc shape, or any other randomly curved shape, and a plurality of bonding portions are parallel to each other. Also, it may have a radial shape or any other shape. And
In such a composite fiber, a thermoplastic resin to which an organic polysiloxane and an antifouling agent are added has a fiber cross section of 2
It is preferable to have an area of 0% or more, and in particular, a part of the thermoplastic resin to which the organic polysiloxane and the antifouling agent are added is exposed on part or all of the fiber surface. It is preferable in terms of the effect of preventing adherence of living things.

Further, the fiber shape of the present invention includes long fibers such as filaments; short fibers such as staples; filament yarns;
Spun yarn; Mixed fiber or blended yarn of the fiber of the present invention and natural fiber, semi-synthetic fiber, other synthetic fiber; plied yarn; natural fiber, synthetic fiber, recycled fiber, glass fiber, metal fiber, carbon fiber, etc. A spun yarn, a filament yarn, or the like is used as a core yarn, and a spun yarn or filament yarn made of the fiber of the present invention is wound around the core yarn in a coil shape, or an organic polysiloxane and A cover coated with a thermoplastic resin to which an antifouling agent is added
, Etc. The fiber of the present invention may be subjected to any treatment such as false twist crimping treatment and entanglement treatment. The fiber product of the present invention may be any of knitted fabrics, non-woven fabrics, final fish nets, ropes, strings and the like made of those fibers and yarns.

Next, the method for producing the fiber of the present invention will be described with reference to an example. When the thermoplastic resin is a polyester such as polyethylene terephthalate, an organic polysiloxane and an antifouling agent are optionally added between the completion of polyester polymerization and immediately before spinning, kneading, and then extruding through a nozzle hole to form a fiber. The method to reduce the viscosity of the resin, side reactions,
It is preferable because problems such as decomposition of the plasticizer do not occur.

When a step of once forming into a pellet shape is obtained after completion of the polyester polymerization, the organic polysiloxane and the antifouling agent may be added after the completion of the weight, and the mixture may be kneaded and stirred to be pelletized, but the viscosity of the resin is lowered. In view of difficulty of uniform dispersion, contamination of the polymerization kettle, etc., at the time of spinning, that is, the organopolysiloxane and the antifouling agent are added to the resin melt fluid obtained by remelting the pellets, and then kneaded by a static mixer. It is preferable to extrude the fibers from the spinning nozzle holes to form fibers. It is not preferable to add the organic polysiloxane and the antifouling agent together with the respective monomers before the polymerization of the polyester, because problems such as side reactions occur.

In the continuous process in which the molten resin is continuously supplied to the spinning nozzle and discharged without passing through the step of pelletizing after the completion of the polymerization of polyester, the melting is performed at an arbitrary stage from the completion of the polymerization to immediately before the spinning. It is preferable that the organic polysiloxane and the antifouling agent are added to the resin, and then the mixture is kneaded with a static mixer and then discharged from the spinning nozzle hole.

When polyolefin is used as the thermoplastic resin, the organic polysiloxane and the antifouling agent may be uniformly kneaded together with the polyolefin into a pellet by a twin-screw kneading extruder, and the pellet may be spun into a fiber. it can.

The fiber thus obtained has an effect of preventing the adhesion of aquatic organisms on the surface of the fiber, even though the contact angle of water on the fiber surface is 90 degrees or more, and further contains an antifouling agent. Therefore, the effect can be sustained for a long period of time. Further, the fibers themselves have strength, durability and flexibility, and are extremely excellent in processability.

The fibers, yarns and fiber products of the present invention are used for fisheries fixed nets used for long-term contact with seawater or freshwater, fish cages for livestock and fisheries, and seawater or freshwater filtration filters. Roads used for mooring buoys, light buoys, buoys, etc.
It can be effectively used as a raw material fiber or a raw material fiber product that constitutes a pollution prevention fiber membrane used for civil engineering.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Physical properties of organic polysiloxane in Examples,
The intrinsic viscosity of polyester and the contact angle of fiber were measured by the following methods. (1) Viscosity of organic polysiloxane (centistokes:
cs) The dynamic viscosity at a predetermined temperature, the intrinsic viscosity ([η]: dl / g) measured with an Ubbelohde viscometer is the density (ρ: g)
Calculated by dividing by / cm ↑ 3). Dynamic viscosity ν (centistokes) = [η] / ρ (2) Sliding angle (degrees) of water in the organopolysiloxane Wire on a ground glass plate-a rod core having a diameter of 0.64 mm-
The organic polysiloxane is uniformly applied using a water filter, and 0.2 ml of distilled water is dripped on the coating film at 25 ° C, 7
The sliding angle of the water droplet was measured using a sliding angle measuring device in a constant temperature and constant humidity of 5% RH. (3) SP value of organic polysiloxane P. A. J. Small, J.M. Appl. Chem. ，
3, 71, (1953). (4) Intrinsic Viscosity of Polyester (dl / g) It was measured by an Uberode viscometer in a constant temperature bath at 30 ° C. using a mixed solvent of phenol and tetrachloroethane. (5) Contact angle (degree) of water on fiber surface A raw material resin is formed into a film, 0.2 ml of distilled water is dripped on the surface, and it is subjected to the tilt plate method in a constant temperature and humidity of 25 ° C. and 75% RH. The contact angle of water was measured.

The adherence of aquatic organisms in Examples and Comparative Examples was visually evaluated according to the following criteria. Twisted yarn for 18 months from April to October of the following year, depth 1 in the Seto Inland Sea
The state of adhesion of marine organisms was examined by immersing it at a position of ~ 2 m. Step status 1: The entire surface area of the twisted yarn is covered with the attached organisms. 2: About 80% of the surface area of the twisted yarn is covered with attached organisms. 3: About 40% of the surface area of the twisted yarn is covered with attached organisms. 4: About 20% of the surface area of the twisted yarn is covered with attached organisms. 5: No attachment of organisms was observed.

Example 1 [η] = 0.6 to which 0.45% by weight of TiO ↓ 2 was added
5 polyethylene terephthalate (hereinafter abbreviated as PET:
The SP value = 8.2) was extruded with a 30Φ extruder and the PE
Viscosity at 25 ℃ is 1000
00 stocks, sliding angle 8.3 degrees and SP value 7.4 dimethyl polysiloxane and metallic copper fine powder having an average particle size of 0.3μ were added so as to be 7% by weight and 3% by weight respectively. (These mixtures are dried in advance at 120 ° C. and defoamed), and then kneaded with a 42 element static mixer (manufactured by Kenix Co., Ltd.) to obtain a die temperature of 295.
It was extruded from a round hole nozzle at ℃ and a take-up speed of 1000 m / min. The spinning raw yarn was drawn 3.5 times with a hot roller at a temperature of 79 ° C. and a hot plate at a temperature of 150 ° C. using a roller plate system, and a denier of 75 denier / 36 filaments was obtained. A filament was obtained. The contact angle of this filament was 101 degrees. Then, the twisted yarn was formed into a rope having a diameter of 6.7 mm, the hardness (rigidity) of the obtained twisted yarn was examined, and a rope having a diameter of 5 cm was produced using this twisted yarn to make it easy to produce. Examined. The results are shown in Table 1. In addition, Table 1 shows the results of observation of the state of adhesion of marine organisms.

Comparative Example 1 Spinning, drawing, twisting and looping were carried out in the same manner as in Example 1 except that fine metal copper powder was not added. The contact angle of the drawn yarn was 101 degrees. Table 1 shows the hardness of the twisted yarn, the easiness of making the rope, and the adhesion state of marine organisms.

Comparative Example 2 Spinning, drawing, twisting and looping were carried out in the same manner as in Example 1 except that dimethylpolysiloxane was not added. The contact angle of the drawn yarn was 86 degrees. The hardness of the twisted yarn,
Table 1 shows the ease of making ropes and the condition of marine organisms attached.
Shown in.

Comparative Example 3 Spinning was carried out in the same manner as in Example 1 except that dimethylpolysiloxane having a viscosity at 25 ° C. of 500 centistokes, a sliding angle of 8.3 degrees and an SP value of 7.2 was used. ,
Stretched, twisted and roped. The contact angle of the drawn yarn is 10
It was 0 degrees. Table 1 shows the hardness of the twisted yarn, the easiness of making the rope, and the adhesion state of marine organisms.

Comparative Example 4 Spinning, drawing, twisting and looping were carried out in exactly the same manner as in Example 1 using PET containing no dimethylpolysiloxane and metallic copper fine powder. The contact angle of the drawn yarn is 16.
It was twice. Table 1 shows the hardness of the twisted yarn, the easiness of making the rope, and the adhesion state of marine organisms.

Example 2 In the same manner as in Example 1 except that nylon 6 (1013B: Ube Industries, Ltd .: SP value = 7.6) was used in place of PET, the die temperature was 295 ° C., the take-up speed was 1000 m.
The spun raw yarn obtained by extruding from a round hole nozzle at a speed of 1 / min is drawn 3.5 times with a hot roller at a temperature of 79 ° C. and a hot plate at a temperature of 150 ° C. using a roller plate system. Then, a multifilament of 75 denier / 36 filaments was obtained. The contact angle of this filament was 98 degrees. Then, the twisted yarn was formed into a rope 1 having a diameter of 6.7 mm, and the hardness (rigidity) of the obtained twisted yarn was examined. I checked. The results are shown in Table 1. In addition, Table 1 shows the results of observation of the state of adhesion of marine organisms.

Example 3 20% by weight of dimethylpolysiloxane having a viscosity of 100,000 centistokes at 25 ° C., a sliding angle of 8.3 degrees and an SP value of 7.4, 2,4,5,6-tetrachloroiso Low-density polyethylene (Sumikasen G804: Sumitomo Chemical Co., Ltd.) containing 20% by weight of phthalonitrile (Nopcoside N-96, manufactured by San Nopco) is 10 times / m single twist yarn and 1000 denier 150 parts by weight per 100 parts by weight of polyester filament of / 192 filament. The contact angle of the coated yarn was 102 degrees. Next, this was twisted into a rope having a diameter of 6.7 mm. The hardness (rigidity) of the obtained twisted yarn was examined, a rope having a diameter of 5 cm was produced using this twisted yarn, and the ease of producing was examined. The results are shown in Table 2. In addition, Table 2 shows the results of observation of the state of adhesion of marine organisms.

Comparative Example 5 Spinning was carried out in the same manner as in Example 3 except that 2,4,5,6-tetrachloroisophthalonitrile was not added.
Stretched, twisted and roped. The contact angle of the drawn yarn is 10
It was 5 degrees. Table 2 shows the hardness of the twisted yarn, the easiness of making the rope, and the state of adhesion of marine organisms.

Comparative Example 6 Spinning, drawing, twisting and looping were carried out in the same manner as in Example 3 except that dimethylpolysiloxane was not added. The contact angle of the drawn yarn was 85 degrees. The hardness of the twisted yarn,
Table 2 shows the ease of making ropes and the condition of marine organisms attached.
Shown in.

Comparative Example 7 Spinning was carried out in the same manner as in Example 3 except that dimethylpolysiloxane having a viscosity at 25 ° C. of 500 centistokes, a sliding angle of 8.3 degrees and an SP value of 7.2 was used. ,
Stretched, twisted and roped. The contact angle of the drawn yarn is 99
It was degree. Table 2 shows the hardness of the twisted yarn, the easiness of making the rope, and the state of adhesion of marine organisms.

Comparative Example 8 Except that dimethylpolysiloxane and low-density polyethylene containing no 2,4,5,6-tetrachloroisophthalonitrile were used as the coating resin, the procedure of Example 3 was repeated.
Spun, drawn, twisted and looped. The contact angle of the drawn yarn was 100 degrees. Table 2 shows the hardness of the twisted yarn, the easiness of making the rope, and the state of adhesion of marine organisms.

Example 4 Instead of 2,4,5,6-tetrachloroisophthalonitrile, 2,4-thiazolyl-benzimidazole (TB
Z: manufactured by Shinto Paint Co., Ltd.) was used, and spinning, drawing, twisting, and forming were performed in the same manner as in Example 3. The contact angle of the drawn yarn was 101 degrees. Table 2 shows the hardness of the twisted yarn, the easiness of making the rope, and the state of adhesion of marine organisms.

Comparative Example 9 Spinning, drawing, twisting and looping were carried out in the same manner as in Example 4 except that dimethylpolysiloxane was not added. The contact angle of the drawn yarn was 86 degrees. The hardness of the twisted yarn,
Table 2 shows the ease of making ropes and the condition of marine organisms attached.
Shown in.

Comparative Example 10 Spinning was carried out in the same manner as in Example 4 except that dimethylpolysiloxane having a viscosity at 25 ° C. of 500 centistokes, a sliding angle of 8.3 degrees and an SP value of 7.2 was used. ,
Stretched, twisted and roped. The contact angle of the drawn yarn is 10
It was 0 degrees. Table 2 shows the hardness of the twisted yarn, the easiness of making the rope, and the state of adhesion of marine organisms.

[0046]

[Table 1]

[0047]

[Table 2]

From the results shown in Tables 1 and 2, the twisted yarn made of the fiber of the present invention has no or extremely little adhesion of marine organisms even after 18 months, and can be used in seawater for a long time. obtain. On the other hand, when only the antifouling agent or the organic polysiloxane having the physical properties out of the range of the present invention is used, the effect of preventing the adhesion of aquatic organisms is insufficient and it cannot be used for a long period of time.

[0049]

The fiber, yarn, and fiber product of the present invention are
It is highly safe to seafood and the human body, has little elution and loss of inclusions from textile products, and is durable, and can prevent aquatic organisms from adhering for a long period of time. The fiber of the present invention,
Since the surface of yarns and textiles is smooth and highly flexible, it does not cause damage to the seafood that has been captured or cultivated, and can be used for twisting, warping, weaving, knitting, rope, etc. The workability at the time is good, and the workability at the time of use is extremely good.

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Claims (2)

[Claims] 1. A polymer which satisfies the following conditions (I) to (III) is 0.1 to 60% by weight, and an antifouling agent is 0.01 to
A fiber made of a thermoplastic resin containing 60% by weight, and having a water contact angle of 90 degrees or more on the fiber surface. (I) Viscosity at 25 ° C is 1000 centistokes or more (II) Water slip angle is 12 degrees or less (III) 2. A fiber product containing the fiber according to claim 1.