JP2001089577A - Structure having effect for preventing attachment of aquatic life - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a structure capable of preventing attachment of an aquatic life. SOLUTION: This structure is constituted of a resin-coated yarn obtained by coating a yarn with a thermoplastic resin containing a bis(2-pyridinethiol-1- oxide)metal salt and an elution amount-controlling substance. In the structure, elution amount of an antifouling agent to sea water is controlled to <=30 mg/cm3 at 25 deg.C and >=3 mg/cm3 at 15 deg.C and flow volume of water under <=18 cm water amount is >=1 cc/cm2.sec.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure used for a long period of time in contact with seawater or freshwater, and more particularly to a structure having an effect of preventing the attachment of aquatic organisms for a long period of time. The present invention also provides, for example, a water-permeable structure capable of preventing aquatic organisms from adhering to a sensor used for measuring water quality for a long period of time and maintaining a measurement environment for acquiring accurate water quality data. About. Furthermore, the present invention has an excellent effect of preventing aquatic organisms from adhering to a ship, and a bottom cover and a screw that can be easily attached / detached by having a filter and water permeability that can stably distribute seawater or freshwater for a long period of time. For covers and the like.

[0002]

2. Description of the Related Art Products used for a long time in seawater or partially in contact with seawater include materials for fisheries such as fixed nets for fisheries, moss nets used for aquaculture, and marine buoys, light buoys, and moorings. There are materials for ships such as buoys, and materials for civil engineering such as pollution prevention films. While these products are in contact with seawater for a long period of time, marine organisms that adhere to the surface thereof, for example, algae such as Aosa diatom, coelenterates such as sea anemone, sponges such as sea sponge, and ring animals such as sea squid, Tactile objects such as bryozoans, mollusks such as mussels, arthropods such as barnacles, and protozoa such as sea squirts attach and inhabit, and the problem that these materials cannot fully fulfill their original functions has arisen. I have.

In recent years, dissolved oxygen in rivers and oceans, p
H, temperature, salinity, ammonia, turbidity and other water quality are continuously measured and monitored, and analyzed to predict the red tide, rapid environmental changes, natural disasters, etc. in advance. Technologies for aquaculture and disaster prevention of fish and shellfish have been studied, and sensors and systems for automatically measuring such data have been developed and are being studied for practical use.

However, when the sensor is continuously immersed in water in order to automatically measure data on water quality, the aquatic creatures described above adhere to the detection part of the sensor, and the sensor is short-lived for a few days. The water quality data becomes abnormal and measurement becomes impossible. For this reason, it was necessary to frequently remove these aquatic organisms or perform repairs such as replacing sensors. In addition, such a measurement system is often installed offshore, requiring a great deal of labor for repair, and has been a hindrance to the spread of the measurement system.

As a countermeasure for preventing the aquatic organisms from adhering to materials and products that come into contact with seawater for a long period of time, the following methods have conventionally been adopted. Conventionally, a method generally used is a method of treating a material or a product with an organotin compound such as tributyltin oxide, triphenyltin hydroxide, triphenyltin acetate, and triphenyltin chloride. However, the method of using these drugs has the harmful effects of intense unpleasant odor and pungent odor during the processing work, and in addition, these drugs accumulate in the body of fish and shellfish and cause obstacles such as malformation and death of fish and shellfish. In addition, it has recently been revealed that the harmful effects on the human body of ingestion are enormous, and there is a tendency for fisheries officials to enter voluntary regulations and become totally banned. Therefore, there is a demand for a new technology that can replace such an organotin compound having a great adverse effect.

As one of such new technologies, there is a method of treating a product with an organic sulfur nitrogen compound such as a urea compound, a benzimidazole compound, a benzothiazole compound, a thiophthalimide compound, or a sulfonylpyridine compound. is there. This method is an attempt to use an organic sulfur-nitrogen compound for aquatic organisms based on the fact that it has been widely used as an agricultural chemical, a fungicide, and a fungicide. It has also been found that these compounds are extremely low-toxic to humans and fish, and are further decomposed into completely non-toxic substances after completing the action of preventing aquatic organisms from adhering. The following method has been proposed as a specific method using an organic sulfur-nitrogen compound having high stability and a high effect of preventing aquatic organisms from adhering.

For example, oily resinous binders include linseed oil, cutting oil, soybean oil, dehydrated castor oil, safflower oil, fish oil and other dry oils, or phenolic resins, oily resinous varnishes, polyhydric alcohols and dicarboxylic acids. This is a method in which an alkyd resin or the like, which is a reaction product, is mixed with an organic sulfur-nitrogen compound to form a coating material, and the product is coated and cured on the product surface. However, the disadvantage of this method is that
Although effective when initially put into the sea, the active ingredients and coating resin components elute or fall off in a relatively short time due to abrasion, etc. due to the weakness of the coating film, and the effect of preventing aquatic organisms from adhering is short term. Is to disappear. As described above, materials using organic sulfur-nitrogen compounds that have a high aquatic organism adhesion prevention effect and have sufficient sustainability have not been obtained in any of the fields of fisheries, ships, and civil engineering. It is the current situation.

[0008] Such a problem also occurs in sensors and filters for measuring water quality used in seawater or freshwater, and in order to solve this problem, an organotin-based antifouling paint is applied to the cover of the sensor. However, it could not be used due to its environmental pollution, toxicity to humans and marine organisms and adverse effects on water quality data. Further, when the antifouling paint is applied to the sensor detecting section itself, there is a problem that the detecting section does not come into contact with water, and the water quality cannot be measured.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a structure capable of preventing the aquatic organisms from adhering to materials used in contact with seawater or freshwater for a long time. Another object of the present invention is to provide a water quality measurement device capable of acquiring accurate water quality data over a long period of time without aquatic organisms adhering to the water quality measurement sensor for a long period of time and without hindering free flow of water near the sensor. It is to provide a water-permeable cover for the sensor. It is a further object of the present invention to provide a filter for seawater or freshwater in which clogging due to aquatic organisms is less likely to occur for a long time. Still further, the present invention provides covers such as a ship bottom cover and a screw cover, which are composed of a water-permeable structure that does not allow aquatic organisms to adhere for a long period of time and has an appropriate water permeability so that the detachable operation can be easily performed. It is to be.

[0010]

Means for Solving the Problems That is, the present invention (first invention)
Is a structure composed of a molded article mainly containing a thermoplastic resin composition containing 0.1 to 20% by weight of a bis (2-pyridinethiol-1-oxide) metal salt, and is preferably a molded article. through the amount of water under the water column 18cm in the 1cc / cm ² · sec
A structure characterized by the presence of the opening described above.

Further, the present invention (second invention) provides a bis (2-pyridinethiol-1-oxide) metal salt of 0.1 to 20%.
It is a structure mainly composed of a fibrous structure made of a thermoplastic resin composition containing 1% by weight, preferably a water column 18
The structure is characterized in that the water flow rate under 1 cm is 1 cc / cm ² · sec or more.

Further, the present invention (third invention) comprises a bis (2-
Pyridinethiol-1-oxide) metal salt in an amount of 0.1 to 2
A structure mainly composed of a fibrous structure at least partially coated or impregnated with a thermoplastic resin composition containing 0% by weight, preferably having a water flow rate of 1 cm under a water column of 18 cm.
It is a structure characterized by being at least cc / cm ² · sec.

More preferably, the present invention is characterized in that, when immersed in artificial seawater, the integrated elution amount of the antifouling agent in the first 10 days is 30 mg / cm ³ or less at 25 ° C. per unit volume of the thermoplastic resin composition. And the structure is ³ mg / cm ³ or more at 15 ° C.

Further, the present invention provides such a structure as a sensor cover for water quality measurement, a filter for seawater or freshwater, a ship bottom cover, a ship screw cover, a wave power type lighthouse cover, and the like.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermoplastic resin composition constituting the structure of the present invention contains bis (2-pyridinethiol-1-).
It is important that a specific amount of an (oxide) metal salt (hereinafter sometimes simply referred to as an antifouling agent) is contained, but the content cannot be determined unconditionally depending on whether the structure is in the form of a form. Is preferably contained in the thermoplastic resin composition in an amount of 0.1% by weight or more in consideration of the effect of preventing adhesion of aquatic organisms. On the other hand, even if the content is excessively large, the improvement of the anti-adhesion effect reaches a plateau, and the problems in the manufacturing process of the structure and the handleability appear, so the upper limit of the content is 50% by weight. Is preferred. A more preferred content is in the range of 3 to 20% by weight. Examples of the metal salt include salts of metals such as copper, zinc, magnesium, calcium, and sodium. Copper salts are most preferably used from the viewpoint of antifouling effect.

Further, other antifouling compounds can be appropriately added as auxiliary components. As auxiliary components, 3-
(3,4-dichlorophenyl) -1,1-dimethylurea, manganese ethylenebisdithiocarbamate, zinc ethylenebisdithiocarbamate, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, cuprous oxide, copper thiocyanate, N- (fluoro Dichloromethylthio) -phthalimide, N- (dichlorofluoromethylthio) -N ′, N′-dimethyl-N-phenylsulfamide, 4,5-dichloro-2-n-octylisothiazolin-3-one, 2,3,5 , 6-tetrachloro-4-methylsulfonylpyridine, 3-iodo-2-propynylbutylcarbamate and the like.

Examples of the thermoplastic resin containing the above antifouling agent include aromatic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyhexamethylene terephthalate (PHMT), polylactic acid, polyethylene succinate and the like. Aliphatic polyesters such as polybutylene succinate, poly-3-hydroxybutylene valerate, and polycaprolactone;
Polyamide such as polycarbonate, nylon 6, nylon 66, nylon 12, nylon 4, and polyphthalamide, polyolefin such as polyethylene and polypropylene, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymethyl methacrylate, polyurethane, Polyisoprene, polybutadiene, SBR, styrene-isoprene elastomer, hydrogenated product thereof, polyester elastomer, polyether elastomer, polyolefin elastomer,
Various elastomers such as polyamide-based elastomers are exemplified.

From the viewpoints of volatilization and thermal decomposition of the antifouling agent at the time of melt molding at a high temperature, uniform kneading with a thermoplastic resin, and the like, in the present invention, a hexahedral mixture of terephthalic acid and 1,6-hexanediol is used. Polyester (PHMT) having a methylene terephthalate unit as a basic unit is preferable, and a polyester obtained by copolymerizing the polyester with isophthalic acid in an amount of 5 to 20 mol% is more preferable in terms of processability, heat melting properties, and the like.

As components to be copolymerized with the polyester, in addition to the above-mentioned isophthalic acid, ethylene glycol,
Diethylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, tricyclodecanedimethanol, polyethylene glycol, polytetramethylene glycol, and other diol components, isophthalic acid, naphthalene-2,6-dicarboxylic acid Acid components such as acid, phthalic acid, α, β- (4-carboxyphenoxy) ethane, 4,4-dicarboxydiphenyl, 5-sodium sulfoisophthalic acid, adipic acid and sebacic acid, and esters thereof. Although the copolymerization ratio is not particularly limited, considering the handling properties of the polymer such as sustained release of bis (2-pyridinethiol-1-oxide) metal salt, crystallinity of polyester, glass transition point, melting point or softening point, etc. The content of each of the diol component and the acid component is preferably in the range of 5 to 50 mol%, particularly 10 to 30 mol%.

The melting point of the thermoplastic resin is preferably 150 ° C. or less, 160 ° C., capillary length 10 mm,
It is preferable that the melt viscosity under a condition of a capillary diameter of 1 mm and a shear rate of 1000 sec ^-1 is 10,000 poise or less. In order to adjust to this condition, the melting point may be lowered by copolymerization as described above, or a melting point depressant such as a medium molecular polymer such as polysiloxane, polybutene, liquid paraffin, or liquid polyester may be appropriately contained. it can.

In the present invention, it is important to control the amount of bis (2-pyridinethiol-1-oxide) metal salt eluted from the structure in order to maintain the effect of preventing aquatic organisms from adhering for a long period of time. is there. Specifically, the artificial seawater (sodium chloride 3%, magnesium chloride 0.5
%, Distilled water 96.5%) is 30 mg / unit at 25 ° C. per unit volume of the thermoplastic resin composition.
cm ^{3 or} less, it is important to at 15 ° C. 3 mg / cm ³ or more, preferably from 3 to 30 mg / cm ³ at 25 ° C., by the at 15 ° C. 3 to 30 mg / cm ³ or more is there.

In order to control the amount of elution, for example, liquid polyolefins such as polybutene and mineral oil, and liquid polyesters (polyester compounds which exhibit fluidity at -50 ° C. to 200 ° C., such as adipic acid, sebacic acid, etc.) An aliphatic dicarboxylic acid component and ethylene glycol, an aliphatic polyester synthesized from a glycol component such as butanediol), a polysiloxane, a phenol resin,
It is preferable to blend a polyphenol such as a phenylphenol resin, a xylenol resin, a butylphenol resin, a resorcinol resin, and a cresol resin, an azine-based compound, and the like in a thermoplastic resin together with an antifouling agent. Also, the amount of the antifouling agent eluted can be controlled as in the present invention by attaching mineral oil, paraffin, polysiloxane, surfactant, resin emulsion, etc. to the surface of the molded product or fiber structure.

In particular, in order to maintain the control of the elution amount for a long period of time, it is preferable that the liquid polyester and the cresol resin are combined and blended in the thermoplastic resin composition.
Further, as the cresol resin, it is preferable to use a novolak type resin from the viewpoint of controlling the elution amount.

The compounding ratio of the compound for controlling the elution amount in the thermoplastic resin composition is determined in relation to the type of the thermoplastic resin, the type of the antifouling agent, and the amount thereof. So it's not a simple decision,
It is preferable that it is blended in the thermoplastic resin composition at a ratio of 1% by weight to 10% by weight.

Further, the above-mentioned thermoplastic resin may appropriately contain a modifier such as an ultraviolet absorber and a crystallization retarder and an additive such as a color pigment.

Next, a method for manufacturing a structure according to the present invention will be described. First, in order to produce a molded article from a thermoplastic resin composition containing a bis (2-pyridinethiol-1-oxide) metal salt, for example, a twin-screw kneading extruder is used to produce a molded article. -Oxide) A metal salt, a compound for controlling the amount of elution, and a thermoplastic resin are uniformly melt-kneaded, and this is extruded from a die slit to produce a film or sheet, or injection molded to obtain a desired product. Or a fiber formed by extruding from a spinning nozzle as described later.

When a three-dimensional structure such as a box or a cylinder is formed from a molded product, a plurality of sheet-shaped molded products may be combined to form a three-dimensional structure. However, in the case of a sheet-like molded product, since there is no water permeability by itself, a hole of a desired size must be formed in the molded product to ensure a desired water flow rate. The pores may be formed mechanically, or may be formed by blending a thermoplastic resin with a substance that can be removed and removed later, and then forming the pores by removing the substance. Means may be used. Further, a mold design having an opening at the molding stage is also possible.

Next, when the thermoplastic resin composition containing the antifouling agent is fiberized, an ordinary melt spinning apparatus can be used as a fiber production apparatus, and the fiber has a circular cross section. It may be any of various shapes and hollow shapes, and the thermoplastic resin containing a bis (2-pyridinethiol-1-oxide) metal salt may appear on at least a part of the fiber surface, preferably 50% or more of the fiber cross-sectional circumference. And then
It is also possible to make a core-sheath type composite fiber or a side-by-side type composite fiber by combining with other thermoplastic resins such as polyester, polyamide, polyolefin, polyvinyl chloride and the like.

When a thermoplastic resin composition containing a bis (2-pyridinethiol-1-oxide) metal salt is coated or impregnated on at least a part of the fiber structure, the fiber structure may be a single fiber (for example, , Monofilament),
Fiber bundle (e.g., spun yarn, multifilament, tow, rope, etc.), nonwoven fabric, woven fabric composed of them,
Knits, nets and the like can be used. The fiber material constituting the fibrous structure is selected from, for example, synthetic fibers, regenerated fibers, natural fibers, metal fibers, glass fibers, carbon fibers, and the like, and the melting point, softening point, or decomposition point is the heat used for coating. It is preferably 50 ° C. or higher than the plastic resin. The fiber structure can be coated or impregnated with a thermoplastic resin composition containing an antifouling agent by various methods. The method of coating or impregnation is not limited, for example, a method of applying a thermoplastic resin composition dissolved in a solvent or the like to the fiber structure, a method of directly extruding the thermoplastic resin composition into a sheet when the thermoplastic resin composition is formed into a sheet. An extrusion coating method in which a film or a sheet is once formed, and a method of heat laminating or dry laminating the fibrous structure may be used.

In the present invention, in particular, in the form of a resin-coated yarn obtained by coating a core yarn with a thermoplastic resin composition containing an antifouling agent, the strength of the obtained structure and the antifouling agent It is preferable from the viewpoint of effective use. As a method for producing the resin-coated yarn, there is a method in which the thermoplastic resin composition is dissolved in a solvent and applied to the surface of the core yarn, but in the present invention,
For example, the raw material is uniformly kneaded using a twin-screw kneader, and a manufacturing process (melting process) as shown in FIG. 3 provided with a pressing die for coating the core yarn with a resin as shown in FIG. Desirable is a method in which a resin containing a bis (2-pyridinethiol-1-oxide) metal salt is directly coated on the surface of the core yarn by extrusion coating method) to produce a resin-coated yarn.

As described above, the material used as the core yarn of the resin-coated yarn is selected from synthetic fibers, regenerated fibers, natural fibers, metal fibers, glass fibers, carbon fibers, and the like. The decomposition point is preferably higher than the thermoplastic resin for coating by 50 ° C. or more, for example,
When a polyhexamethylene terephthalate-based polyester is used as the coating resin, the core yarn is preferably made of polyethylene terephthalate fiber. In addition, the form of the core yarn is not particularly limited, regardless of monofilament, multifilament, spun yarn, etc.
Further, a twisted yarn or the like made of these can be used as necessary.

Next, a molded article comprising the thermoplastic resin composition,
A method for producing a structure using a fiber structure and a resin-coated fiber structure will be described. First, in the case of manufacturing a structure from a molded product such as a sheet, it can be manufactured by extruding a thermoplastic resin composition containing an antifouling agent into a mold having a shape of an end use. It is good also as a structure of a desired shape by combining sheets. However, in applications requiring water permeability, it is necessary to provide an opening in the sheet molded product by post-processing or to form the opening in the design stage of the mold.

Next, the case of producing a fiber structure will be described. A woven fabric, a knitted fabric, a nonwoven fabric, and a composite material obtained by laminating these fibers have a characteristic of having water permeability by themselves, and in applications where water permeability is required,
It is preferably used as a fibrous structure. Further, the fiber structure is more flexible than a thick sheet-like molded product, so that the fiber structure is still more suitable for applications that are used along a curved surface or a complicated shape.

In the case of a woven fabric, a weaving loom such as a shuttle loom, a rapier loom, an air jet loom, a gripper loom can be used, and the weaving structure is not particularly limited. You can use satin weave or the like,
In order to set the amount of water flow under a water column of 18 cm to the target value of the present invention, it is necessary to appropriately select the woven densities of the warp and the weft, the respective yarn deniers, and the like.

As a method for obtaining a knitted fabric, a knitted fabric such as a warp knitted inlay knit, a pile knit, and a weft-inserted Russell knit can be manufactured by a Russell machine or a tricot machine.
A knit can also be obtained by weft knitting, stitch bonding and braiding. Further, the nonwoven fabric can be formed by various manufacturing techniques such as a wet method, a dry method for forming a card web, a spun bond method, and a melt blow method.

In the present invention, when a composite of a thermoplastic resin and a fibrous structure is used, at least one of the thermoplastic resin layer and the fibrous structure contains bis (2-pyridinethiol-
It suffices if a 1-oxide) metal salt is contained. However, since the water permeability of these composite structures is lost or extremely low due to the thermoplastic resin, it is necessary to provide an opening so that the structure has a desired water flow depending on the use.

Further, the structure of the present invention may be composed of a molded article, a fibrous structure, or a resin-coated fibrous structure having an effect of preventing aquatic organisms from adhering thereto, provided that the effects of the present invention are not impaired. Mixing or combining other resin moldings, inorganic materials, synthetic fibers, inorganic fibers, natural fibers, and the like that do not have the aquatic organism adhesion preventing function can be used. At this time, the ratio between the two needs to be changed depending on the strength of the effect of preventing aquatic organisms from adhering, but it cannot be determined unconditionally. Is desirable. The form of mixing or compounding is not particularly limited, but in the case of a fiber structure, means such as mixed fiber, mixed spinning, ply twisting, weaving, weaving and the like can be adopted. In addition, heat treatment may be appropriately performed on the fiber structure to fuse the intersections between the fibers, thereby improving the strength and preventing misalignment.

In the present invention, the form of the structure is particularly limited.
Not specified, but water column is required for applications requiring water permeability
1cc / cm of water flow under 18cm^Two・ Preferably longer than sec
5cc / cm depending on the application^Two・ Sec or more, further 10cc / cm^Two・
sec or more, preferably 15cc / cm ^Two・ Set to more than sec
Can be.

Here, the measurement of the amount of water passing through the water-permeable structure is measured using an apparatus as shown in FIG. In FIG. 1, a water supply port 2 is provided at an upper side of a cylindrical container 1.
Is provided, an opening 4 is provided in the cylindrical container bottom 3,
A water-permeable structure A is fixed to the opening 4, and a drain port 5 is provided on the side surface of the cylindrical container corresponding to a height of 18 cm from the surface of the structure A. In order to maintain the water column of the height of, the excess water that always overflows from the drain port is supplied from the water supply port, and the amount of water that falls through the structure in such a state is determined. / cm ²
・ It is displayed in the unit of sec.

The present inventors have proposed a water quality measurement sensor,
To monitor water quality data stably and accurately for a long period of time, in order to accurately measure the quality of seawater and freshwater in the process of conducting various studies by covering the sensor so that aquatic organisms do not adhere to it, It was found that accurate water quality data could not be obtained unless the water to be measured was constantly flowing near the sensor, not to mention that no organisms adhered to the detection unit. In order to ensure an effective concentration that can prevent the attachment of aquatic organisms without inhibiting the water quality, the water flow rate of the water quality measurement sensor cover is preferably 15 cc / cm ² sec or more,
Further, they have found that 15 to 200 cc / cm ² · sec is a preferable range. If the water flow rate is less than 15 cc / cm ² · sec, the presence of the cover will affect the true water quality near the sensor, making accurate water quality measurement impossible. On the other hand, if the flow rate is too large, it is not possible to secure an effective antifouling agent concentration environment for suppressing the adhesion of aquatic organisms, and the aquatic organisms are likely to adhere to the sensor. Furthermore, in order to accurately measure turbidity other than dissolved oxygen in water quality measurement, 100 to 2
It is preferable to use a structure having a water permeability of 00 cc / cm ² · sec.

The form of the cover is not particularly limited as long as the above-mentioned water flow rate can be exhibited, and a cover for covering the housing for protecting the sensor may be used. Noren-like shape where a number of strip-shaped moldings and strings are arranged in parallel and their ends are connected
It can be in the form of a (shape). In applications where high precision such as water quality measurement is not required and the effect of preventing aquatic organisms from attaching is prioritized, the water flow rate is 5 cc / cm ² · s.
It should be ec or more.

Further, the structure of the present invention can be applied to a filter installed in a seawater intake section used for cooling in a thermal power plant, a nuclear power plant, or the like, or a pesticide in a golf course, in addition to a cover for a water quality measurement sensor. It is also used effectively as a filter for seawater or freshwater, such as a filter for adsorptive filtration of pesticides from wastewater containing water, in which case 5 cm
The water flow rate under the water column is 10 cc / cm ² · sec or more, preferably 1
It is preferably 5 to 50 cc / cm ² · sec. 1 water flow
If the flow rate is less than 0 cc / cm ² · sec, the resistance is too large when a large amount of cooling water is required, while if the flow rate is too large,
An effective concentration of an antifouling agent for suppressing the adhesion of aquatic organisms cannot be secured, and for example, aquatic organisms are likely to adhere to cooling pipes.

In the present invention, for applications requiring water permeability as described above, the fiber structure is preferably used in view of easy control of water flow, ease of production, product strength, dimensional stability, and the like. Is preferably a mesh fabric. In that case, besides the amount of water passing, the absolute value of the mesh opening of the fabric is 10 to 3
It is preferable to use a woven fabric of about 0 mesh from the viewpoint of a filter effect and the like.

Further, the fiber structure of the present invention is used as a cover for a flooded portion of a ship bottom structure such as a ship bottom and a screw, and prevents aquatic organisms from adhering to the ship bottom and the ship bottom structure. It has a feature that aquatic organisms do not adhere to itself. The ship bottom cover of the present invention has a water flow rate of 1 cc / cm ² · sec under a water column of 18 cm.
Or more, preferably 5 cc / cm ² · sec or more, more preferably 1 cc / cm ² · sec or more.
It is important that the water flow rate is 0 cc / cm ² · sec or more.If the water flow under 18 cm of water column is less than 1 cc / cm ² · sec, the water permeability of the cover is not sufficient when attaching and detaching the bottom cover. But the workability is reduced.

Further, the structure of the present invention can be used for various purposes. For example, it can be used as a fixed net, a fish net for aquaculture, a rope for tailoring the net, or a rope for mooring. it can. In applications where water permeability is not required, it is also possible to cover a flooded portion of an underwater structure or building as a high-density woven fabric or the like to prevent aquatic organisms from adhering. As a specific application as described above, it can be suitably used for a cover of a flooded portion of a wave power type lighthouse (buoy) and the like.

By using the structure of the present invention for a cover or filter of a water quality sensor, a ship bottom cover, etc., conventionally, aquatic organisms are attached within a few days from the start of use, and it is necessary to clean and replace it quite frequently. In the above-mentioned applications, it was confirmed that the effect of preventing the attachment of aquatic organisms for several months or more, and maintaining an accurate water quality measurement environment, a smooth water flow, and easy attachment / detachment was confirmed.

[0047]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In addition, each evaluation and measurement in an Example are performed by the following methods.

Aquatic organisms attached to sensors Multi-item water quality monitor "model 6000 (YSI, D8.
9cm x L49.5cm) ", and immersed in the water at a depth of 15m in Shirahama, Wakayama Prefecture, and periodically observed the state of aquatic organisms attached to the sensor detection unit. evaluated. Criteria 5: No adhesion of organisms was observed. 4: Adherence of organisms was observed on about 10% of the entire surface of the object. 3: Adherence of organisms was observed on about 20% of the entire surface of the object. 2: Adherence of organisms was observed on about 50% of the entire surface of the object. 1: Adherence of organisms was observed on the entire surface of the object.

Dissolved oxygen, pH Measured continuously by a water quality measurement system connected to "model 6000".

The status of aquatic organisms adhering to the bottom cover of a ship A 7 m long pleasure boat moored in the Seto Inland Sea was covered with the bottom cover, and the status of aquatic organisms adhering to the bottom and the bottom cover was evaluated according to the following criteria. . 5: No attachment of organisms was observed. 4: Adherence of organisms was observed on about 10% of the entire surface of the object. 3: Adherence of organisms was observed on about 20% of the entire surface of the object. 2: Adherence of organisms was observed on about 50% of the entire surface of the object. 1: Adherence of organisms was observed on the entire surface of the object.

Aquatic organisms attached to knotless nets and ropes The aquatic organisms were immersed in the Seto Inland Sea and evaluated for adherence to the following criteria. 5: No attachment of organisms was observed. 4: Adherence of organisms was observed on about 10% of the entire surface of the object. 3: Adherence of organisms was observed on about 20% of the entire surface of the object. 2: Adherence of organisms was observed on about 50% of the entire surface of the object. 1: Adherence of organisms was observed on the entire surface of the object.

The elution amount of the antifouling agent The specific gravity of the thermoplastic resin composition containing the antifouling agent was measured with an electronic densitometer SD-120L (Mirage Trading). 0.5 g of the composition is collected, and artificial seawater (completely dissolved in 36.5% of sodium chloride and 0.5% of magnesium chloride in 96.5% of distilled water) is 300 m.
and stirred in a thermostat at 25 ° C. and 15 ° C. at 65 rpm. Every 24 hours, the artificial seawater was replaced with a new one, and the immersed artificial seawater was collected and analyzed by HPLC (High Perfor
The elution amount of the antifouling agent was measured by mance liquid chromatography, and the measurement was performed for 10 days, and the integrated value for 10 days was obtained.

Fish toxicity evaluation 20 liters of seawater was placed in a 30 liter water tank, and 0.5 g of a sample was prepared under the conditions of a water temperature of 25 ° C. and 90% or more of dissolved oxygen.
Five red sea bream (4 cm in body length) were fed and reared for 48 hours, and the growth state of the test fish was observed.

Example 1 Polyhexamethylene terephthalate prepared by copolymerizing isophthalic acid at 10 mol% (melting point: 135 ° C., melt viscosity: 3,500 po
ise) and bis (2-pyridinethiol-1-oxide)
Copper salt was contained at 10% by weight, polybutene having an average molecular weight of 3,000 (Idemitsu Petrochemical Co., Ltd., 2000H) at 6% by weight, and a black pigment made of carbon at 0.4% by weight, and the apparatus shown in FIGS. 2 and 3 was used. 100 parts by weight of polyethylene terephthalate filament (500d / 96f, 120T / m single twist), 200 parts by weight,
00 denier resin-coated yarn was obtained.

From the obtained resin-coated yarn, using a rapier loom, plain weave, length 1500d 15 / inch, width 1500d 15
A woven fabric having a mesh size of 16 meshes per inch was obtained. This was heated to 125 ° C. ×
The intersection was thermally fused at a processing speed of 1.5 minutes. The water passing amount of the obtained woven fabric was 50 cc / cm ² · sec.

Next, this was cut into 30 cm × 65 cm,
The whole “model 6000” was covered and immersed in the sea of Shirahama, Wakayama Prefecture, and the dissolved oxygen and pH were continuously measured, and the state of attachment of aquatic organisms was observed. The results are shown in Table 1. No organisms adhered to the sensor detection part for 2 months, and no abnormality was observed in the dissolved oxygen and pH data.

[0057]

[Table 1]

Example 2 The method of Example 1 was repeated except that the weaving density was adjusted to 1500 d25.
A plain woven fabric was obtained in the same manner as in Example 1, except that the openings were 26 mesh and the water flow rate was 27 cc / cm ² · sec. This was coated on a water quality monitor model 6000, the dissolved oxygen and pH were measured in the sea of Shirahama, and the state of adhesion of aquatic organisms was observed. The results are shown in Table 1. No organisms adhered to the sensor detection part for 2 months, and no abnormality was observed in the dissolved oxygen and pH data.

Example 3 The method of Example 2 was repeated except that the weft was 1500d / 288f.
In the same manner as in Example 1 except that the polyethylene terephthalate yarn was changed to a plain woven fabric having a mesh size of 16 mesh and a water flow rate of 14 cc / cm ² · sec. This is a water quality monitor
model 6000, dissolved oxygen and p in the sea of Shirahama
H was measured and the state of adhesion of aquatic organisms was observed. The results are shown in Table 1. No organisms adhered to the sensor detection part for 2 months, and no abnormality was observed in the dissolved oxygen and pH data.

Example 4 The procedure of Example 1 was repeated, except that 10 mol% of isophthalic acid-modified polyhexamethylene terephthalate was changed to low density polyethylene (melting point: 105 ° C., melt viscosity: 3000 poise). A plain fabric having an opening of 16 mesh and a flow rate of 50 cc / cm ² · sec was obtained. This was coated on a water quality monitor model 6000, the dissolved oxygen and pH were measured in the sea of Shirahama, and the state of adhesion of aquatic organisms was observed. The results are shown in Table 1. No organisms adhered to the sensor detection part for 2 months, and no abnormality was observed in the dissolved oxygen and pH data.

Example 5 Polyhexamethylene terephthalate prepared by copolymerizing 15 mol% of adipic acid (melting point: 132 ° C., melt viscosity: 3000 poise)
6% by weight of bis (2-pyridinethiol-1-oxide) copper salt, 3- (3,4-dichlorophenyl) -1,
4 wt% of 1-dimethylurea, 6 wt% of polybutene having an average molecular weight of 3,000 (made by Idemitsu Petrochemical Co., Ltd., 2000H), and 0.4 wt% of a black pigment made of carbon were mixed and kneaded with a twin screw extruder. Discharge from die 0.2 thickness
A 0 mm antifouling resin film was obtained. The film was heat-laminated on both sides of a plain woven fabric (500d / 96f, 150T / m single twisted yarn, density length 25 / inch, width 25 / inch) using a polyethylene terephthalate filament to obtain an antifouling tarpaulin. Obtained. A hole having a diameter of 6 mm was formed every 1 cm in the vertical and horizontal directions of the tarpaulin to obtain a tarpaulin having a water flow rate of 48 cc / cm ² · sec. This is coated on a water quality monitor model 6000, the dissolved oxygen and pH are measured in the sea of Shirahama, and the state of attachment of aquatic organisms is observed.
The results are shown in Table 1. No organisms adhered to the sensor detection part for 2 months, and no abnormality was observed in the dissolved oxygen and pH data.

Example 6 Polyhexamethylene terephthalate copolymerized with 30 mol% of butanediol (melting point: 126 ° C., melt viscosity: 4000 p
oise) to bis (2-pyridinethiol-1-oxide)
6% by weight of copper salt, 3- (3,4-dichlorophenyl)-
4% by weight of 1,1-dimethylurea, average molecular weight 300
6% by weight of polybutene (2000H, manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.4% by weight of a black pigment made of carbon, kneaded by a twin-screw extruder, and discharged from a T-die to have a thickness of 0.1%.
A 5 mm antifouling resin film was obtained. A hole of 6 mm is made every 1 cm in the vertical and horizontal directions of the film, and the water flow is 48 cc.
/ cm ² · sec. This is water quality monitor model6
000, measured dissolved oxygen and pH in the sea of Shirahama, and observed the status of aquatic organisms attached.
It was shown to. Aquatic organisms did not adhere to the sensor detector for 2 months, and there was no abnormality in dissolved oxygen and pH data.

Example 7 Polybutene having an average molecular weight of 3000 and polybutene having a weight average molecular weight of 10% by weight of bis (2-pyridinethiol-1-oxide) copper salt in polyhexamethylene terephthalate obtained by copolymerizing 10% by mole of isophthalic acid (Idemitsu Petrochemical Co., Ltd.) 2000H) and 0.4% by weight of a carbon black pigment.
The mixture was kneaded with a φ twin screw extruder, discharged from a round hole nozzle and spun. The spun yarn was drawn by a roller plate method using a hot roller at 40 ° C., a hot plate at 75 ° C., and a draw ratio of 3.5 times to obtain a multifilament of 500 dr / 96f. This was twisted at 150 T / m, and woven by plain weaving using a rapier loom to a length of 15 / inch and a width of 15 / inch to obtain a woven fabric with a basis weight of 16 mesh. The water passing amount of the obtained woven fabric was 24 cc / cm ² · sec. This was coated on a water quality monitor model 6000, and dissolved oxygen and pH were measured in the sea of Shirahama.
Was measured, and the state of attachment of aquatic organisms was observed. The results are shown in Table 1. Aquatic organisms did not adhere to the sensor detector for 2 months, and there was no abnormality in dissolved oxygen and pH data.

Example 8 The antifouling agent was bis (2-pyridinethiol-1-oxide).
A structure was prepared in the same manner as in Example 1 except that a zinc salt was used and a compound as shown in Table 2 was added to the thermoplastic resin in order to control the elution amount of the antifouling agent. Done. Table 2 shows the results.

[0065]

[Table 2]

Example 9 The antifouling agent was bis (2-pyridinethiol-1-oxide).
A structure was prepared in the same manner as in Example 2 except that a zinc salt was used and a compound as shown in Table 2 was mixed with the thermoplastic resin in order to control the amount of the antifouling agent eluted. Done. Table 2 shows the results.

Example 10 The antifouling agent was bis (2-pyridinethiol-1-oxide).
A structure was prepared in the same manner as in Example 3 except that a zinc salt was used and a compound as shown in Table 2 was mixed with the thermoplastic resin in order to control the amount of the antifouling agent eluted. Done. Table 2 shows the results.

Example 11 The antifouling agent was bis (2-pyridinethiol-1-oxide).
A structure was prepared in the same manner as in Example 4 except that a compound as shown in Table 2 was added to the thermoplastic resin in order to control the elution amount of the antifouling agent as a zinc salt. Done. Table 2 shows the results.

Example 12 The antifouling agent was bis (2-pyridinethiol-1-oxide).
A structure was prepared in the same manner as in Example 5 except that a zinc salt was used and the composition was as shown in Table 2 in order to control the elution amount of the antifouling agent, and the structure was evaluated in the sea. Table 2 shows the results.

Example 13 The antifouling agent was bis (2-pyridinethiol-1-oxide).
A structure was prepared in the same manner as in Example 6 except that a zinc salt was used and a compound as shown in Table 2 was added to the thermoplastic resin in order to control the elution amount of the antifouling agent. Done. Table 2 shows the results.

Example 14 The antifouling agent was bis (2-pyridinethiol-1-oxide).
A structure was prepared in the same manner as in Example 7 except that a compound as shown in Table 2 was added to the thermoplastic resin in order to control the elution amount of the antifouling agent as a zinc salt. Done. Table 2 shows the results.

Comparative Example 1 Dissolved oxygen and pH were measured in the sea of Shirahama using a water quality monitor model 6000 without covering. Abnormal values began to appear on the third day, and became unmeasurable one week later. As a result of pulling up and observing, a large amount of aquatic organisms adhered to the entire monitor and completely covered the sensor section.

Example 15 12 parts by weight of bis (2-pyridinethiol-1-oxide) copper salt and cresol novolak were added to 100 parts by weight of polyhexamethylene terephthalate (melting point: 135 ° C.) obtained by copolymerizing 10% by mole of isophthalic acid. 8 parts by weight of resin (average degree of polymerization: 3.6), 0.5 part by weight of carbon black, and 100 parts by weight of polyethylene terephthalate filament (500 d / 96 f, 120 T / m single twist), 200 parts by weight of this resin composition 1 part by weight
A resin-coated yarn of 500 denier was obtained. From the obtained resin-coated yarn, a knotless knitting machine was used to produce a 24000d / 16 knotless knotted net of 6 knots and was immersed in Seto Inland Sea Mushiaki Bay. As a result of the toxicity evaluation, the test fish continued to grow for 48 hours. In addition, as a result of measuring the elution amount during the initial 10 days, 25 ° C .; 15.9 mg / c
m ³ , 15 ° C .; 10.3 mg / cm ³ .

Example 16 Bis (2-pyridinethiol-1-oxide) copper salt was added to 6
Parts and cresol novolak resin were changed to 4 parts to obtain a resin-coated yarn of 1500 denier in the same manner as in Example 15. A knotless net is made from the obtained resin-coated yarn,
When immersed in Seto Inland Sea Insect Mystery Bay, the antifouling effect was maintained for more than one year, and the fish toxicity was evaluated. As a result, the test fish continued to grow for 48 hours. In addition, as a result of measuring the elution amount for the first 10 days, 25 ° C; 12.3 mg / cm ³ , 15 ° C;
g / cm ³ .

Example 17 Bis (2-pyridinethiol-1-oxide) copper salt was added to 6
Example 15 except that 8 parts by weight and 8 parts by weight of cresol novolak resin were changed to 6 parts by weight of polybutene (average molecular weight: 3000).
In the same manner as in the above, a 1500 denier resin-coated yarn was obtained. A knotless net was prepared from the obtained resin-coated yarn and immersed in Seto Inland Sea Mushimei Bay. The antifouling effect was maintained for more than one year, and the fish toxicity was evaluated. As a result, the test fish continued to grow for 48 hours. Was. Also, as a result of measuring the elution amount during the initial 10 days, 25 ° C .;
7.7 mg / cm ³ , 15 ° C .; 7.6 mg / cm ³ .

Example 18 The procedure of Example 15 was repeated, except that the polyhexamethylene terephthalate copolymerized with 10 mol% of isophthalic acid was changed to the polyhexamethylene terephthalate copolymerized with 10 mol% of methylpentanediol. A denier resin-coated yarn was obtained. A knotless net was prepared from the obtained resin-coated yarn and immersed in Seto Inland Sea Mushiaki Bay.
The antifouling effect has been maintained for more than one year, and fish toxicity has been evaluated.
The test fish continued to grow for 8 hours. In addition, as a result of measuring the elution amount during the initial 10 days, 25 ° C .; 14.6 mg / cm ³ ,
15 ° C; 10.2 mg / cm ³ .

Example 19 Polyhexamethylene terephthalate obtained by copolymerizing isophthalic acid at 10 mol% was converted to low-density polyethylene (melting point: 115
° C) except that the temperature was changed to 150 ° C.
0 denier resin-coated yarn was obtained. A knotless net was prepared from the obtained resin-coated yarn and immersed in Seto Inland Sea Mushimei Bay. The antifouling effect was maintained for more than one year, and the fish toxicity was evaluated. As a result, the test fish continued to grow for 48 hours. Was. In addition, as a result of measuring the elution amount during the initial 10 days, 25 ° C .; 28.4 mg / c
m ³ , 15 ° C .; 12.6 mg / cm ³ .

Example 20 12 parts by weight of bis (2-pyridinethiol-1-oxide) copper salt and cresol novolak were added to 100 parts by weight of polyhexamethylene terephthalate (melting point: 135 ° C.) obtained by copolymerizing 10% by mole of isophthalic acid. A resin (average degree of polymerization: 3.6) containing 8 parts by weight of carbon black and 0.5 parts by weight of carbon black, and a Labo Plastomill film molding machine (Toyo Seiki)
Was used to produce a film having a thickness of 300 μm. This film was cut into a tape having a width of 1 cm, and was uniformly wound on a rope having a diameter of 6 mm, and subjected to a heat fusion treatment at 120 ° C. for 5 minutes. When the obtained rope was immersed in Seto Inland Sea Mushiaki Bay, the antifouling effect was maintained for one year or more. As a result of collecting 0.5 g of the film and evaluating the toxicity of the fish, the test fish continued to grow for 48 hours. In addition, the initial 10
As a result of measuring the amount of elution per day, 25 ° C .; 15.9 mg /
cm ³ , 15 ° C .; 10.3 mg / cm ³ .

EXAMPLE 21 12 parts by weight of bis (2-pyridinethiol-1-oxide) zinc salt and cresol novolak were added to 100 parts by weight of polyhexamethylene terephthalate (melting point: 135 ° C.) obtained by copolymerizing 10% by mole of isophthalic acid. A resin (average degree of polymerization 3.6) of 8 parts by weight and carbon black of 0.5 parts by weight are contained, and a polyethylene terephthalate filament (500 d / 96) is prepared by using the apparatus shown in FIGS.
f, 120 T / m single twist) 200 parts per 100 parts by weight
By weight, the resin-coated yarn of 1500 denier was obtained. From the obtained resin-coated yarn, use a knotless knitting
When a non-knotted net of 00d / 16 lines and 6 sections was prepared and immersed in Seto Inland Sea Mushimei Bay, the antifouling effect was maintained for more than 1 year and the fish toxicity was evaluated. As a result, the test fish grew for 48 hours. Continued. Further, as a result of heat fusing in a state where the twisted shape was maintained, 0.5 g of a knotless net was sampled and the elution amount during the initial 10 days was measured, and as a result, 25 ° C; 15.9 mg / cm ³ , 15 ° C;
It was ³ mg / cm ³ .

Example 22 A resin-coated yarn of 1500 denier was obtained in the same manner as in Example 15 except that the bis (2-pyridinethiol-1-oxide) zinc salt was changed to 6 parts and the cresol novolak resin was changed to 4 parts. Was. A knotless net was prepared from the obtained resin-coated yarn and immersed in Seto Inland Sea Mushimei Bay. The antifouling effect was maintained for more than one year, and the fish toxicity was evaluated. As a result, the test fish continued to grow for 48 hours. Was. In addition, as a result of measuring the elution amount during the initial 10 days, 25 ° C; 12.3 mg / cm ³ , 15 ° C;
It was 6 mg / cm ³ .

Example 23 Same as Example 15 except that bis (2-pyridinethiol-1-oxide) zinc salt was changed to 6 parts and cresol novolak resin 8 parts to polybutene (average molecular weight 3000) 6 parts. To obtain a resin-coated yarn of 1500 denier. A knotless net was prepared from the obtained resin-coated yarn and immersed in Seto Inland Sea Mushimei Bay. The antifouling effect was maintained for more than one year, and the fish toxicity was evaluated. As a result, the test fish continued to grow for 48 hours. Was. In addition, as a result of measuring the elution amount for the initial 10 days,
25 ° C; 17.7 mg / cm ³ , 15 ° C; 7.6 mg / cm
cm ³ .

Example 24 1500 denier was prepared in the same manner as in Example 21 except that polyhexamethylene terephthalate obtained by copolymerizing 10% by mole of isophthalic acid was changed to polyhexamethylene terephthalate obtained by copolymerizing 10% by mole of methylpentanediol. Was obtained. A knotless net was prepared from the obtained resin-coated yarn and immersed in Seto Inland Sea Mushimei Bay. The antifouling effect was maintained for more than one year, and the fish toxicity was evaluated. As a result, the test fish continued to grow for 48 hours. Was. Further, as a result of measuring the elution amount during the initial 10 days, 25 ° C .; 14.6 mg / cm ³ , 15
° C; 10.2 mg / cm ³ .

Example 25 Polyhexamethylene terephthalate obtained by copolymerizing isophthalic acid at 10 mol% was converted to low-density polyethylene (melting point: 115
° C), except that the temperature was changed to 150 ° C.
0 denier resin-coated yarn was obtained. A knotless net was prepared from the obtained resin-coated yarn and immersed in Seto Inland Sea Mushimei Bay. The antifouling effect was maintained for more than one year, and the fish toxicity was evaluated. As a result, the test fish continued to grow for 48 hours. Was. In addition, as a result of measuring the elution amount during the initial 10 days, 25 ° C .; 28.4 mg / c
m ³ , 15 ° C .; 12.6 mg / cm ³ .

Example 26 12 parts by weight of bis (2-pyridinethiol-1-oxide) zinc salt and cresol novolak were added to 100 parts by weight of polyhexamethylene terephthalate (melting point: 135 ° C.) obtained by copolymerizing 10% by mole of isophthalic acid. A film having a thickness of 300 μm was prepared using a Labo Plastomill film molding machine (Toyo Seiki) containing 8 parts by weight of resin (average degree of polymerization 3.6) and 0.5 part by weight of carbon black. This film is cut into a tape having a width of 1 cm and has a diameter of 6 mm.
Was uniformly wound in a single winding and subjected to a heat fusion treatment at 120 ° C. for 5 minutes. When the obtained rope was immersed in Seto Inland Sea Mushiaki Bay, the antifouling effect was maintained for one year or more. As a result of collecting 0.5 g of the film and evaluating the toxicity of the fish, the test fish continued to grow for 48 hours. Further, as a result of measuring the elution amount of the film for the first 10 days, 25 ° C .; 15.9 m
g / cm ³ , 15 ° C .; 10.3 mg / cm ³ .

[Brief description of the drawings]

FIG. 1 is a schematic view of an apparatus for measuring a water flow rate of a water-permeable structure.

FIG. 2 is a sectional view of a pressing die of an apparatus for manufacturing a resin-coated yarn.

FIG. 3 is a conceptual diagram of a manufacturing process of a resin-coated yarn.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cylindrical container 2 Water supply port 3 Cylindrical container bottom 4 Opening 5 Drainage port A Water-permeable structure

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/16 C09D 5/16 7/12 7/12 Z 201/00 201/00 E02B 1/00 301 E02B 1/00 301B F-term (reference) 4F071 AA14 AA18 AA21 AA41 AA43 AA45 AA67 AA81 AC19 AF55 AH02 AH19 BA01 BB06 BC02 BC05 BC07 4H011 AD01 BA01 BC19 DA10 DA11 DC10 DH02 DH04 DH07 DH27 4J002 AC031 BB1BC021 CC032 CC042 CC052 CC062 CE002 CE003 CF002 CF003 CF051 CF061 CF071 CF181 CG001 CK021 CL011 CL031 EV086 FD186 GF00 GL00 GN00 4J038 CB001 CB002 DA041 DA042 DA051 DA052 DA071 DA072 DA101 P102 DL03 DD10 DD03 DD07

Claims (18)

[Claims] 1. A method for preventing aquatic organisms from adhering, comprising a molded article mainly containing a thermoplastic resin composition containing 0.1 to 20% by weight of a bis (2-pyridinethiol-1-oxide) metal salt. A structure that has an effect. 2. An aquatic organism comprising mainly a fibrous structure comprising a thermoplastic resin composition containing 0.1 to 20% by weight of a bis (2-pyridinethiol-1-oxide) metal salt. A structure having an adhesion preventing effect. 3. A fibrous structure comprising a thermoplastic resin composition containing 0.1 to 20% by weight of a bis (2-pyridinethiol-1-oxide) metal salt at least partially coated or impregnated with a fiber structure. A structure having an aquatic organism adhesion preventing effect. 4. The flow rate of water through a molded product under a water column of 18 cm is 1 cc / c.
The structure according to claim 1, wherein an opening having a length of m ² · sec or more is present. 5. The structure according to claim ² , wherein a water flow rate under a water column of 18 cm is 1 cc / cm ² · sec or more. 6. The structure according to claim 3, wherein a water flow rate under a water column of 18 cm is 1 cc / cm ² · sec or more. 7. The structure according to claim 3, wherein the fibrous structure at least partially coated or impregnated with the thermoplastic resin composition is a resin-coated yarn. 8. The structure according to claim 3, wherein the fibrous structure at least partially coated with or impregnated with the thermoplastic resin composition is a resin processed cloth. 9. The structure according to claim 2, wherein the structure is based on a mesh fabric or a mesh fabric.
The structure according to any one of the above. 10. The flow rate under a water column of 18 cm is 15 cc / cm ² · s.
The structure according to any one of claims 1 to 9, which is a cover for a water quality measurement sensor of ec or more. 11. The flow rate under a water column of 18 cm is 10 cc / cm ² · s.
The structure according to any one of claims 1 to 9, which is a filter for seawater or freshwater of ec or more. 12. The flow rate under a water column of 18 cm is 1 cc / cm ² · sec.
The structure according to any one of claims 2, 3, 5 to 9, wherein the structure is the above bottom cover. 13. The structure according to claim 2, which is a cover for a ship screw. 14. The structure according to claim 2, which is a cover for a wave-powered lighthouse. 15. When immersed in artificial seawater, the integrated elution amount of the antifouling agent for the first 10 days is 30 mg / cm ³ or less at 25 ° C. per unit volume of the thermoplastic resin composition, and
The structure according to any one of claims 1 to 14, wherein the structure is ³ mg / cm ³ or more at 5 ° C. 16. A thermoplastic resin comprising terephthalic acid and 1,1,
The structure according to any one of claims 1 to 15, which is a polyester having a hexamethylene terephthalate unit composed of 6-hexanediol as a basic skeleton. 17. A thermoplastic resin composition comprising a liquid polyolefin, a liquid polyester, a polysiloxane, a phenol resin, a phenylphenol resin, a xylenol resin,
The structure according to any one of claims 1 to 16, further comprising at least one compound selected from the group consisting of a butylphenol resin, a resorcin resin, a cresol resin, and an azine compound. 18. A thermoplastic resin composition comprising a liquid polyester and a cresol resin.
8. The structure according to any one of items 7 to 7.