JPH10337132A - Fish or shell-breeding net - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject fish or shell-breeding net that is durable and can continuously manifest antifouling effect against aquatic life for a long period of time by forming the twist-knitted stitch parts by using a yarn coated with a thermoplastic resin containing a specific compound. SOLUTION: The twisted stitch parts are formed with a coated yarn with a thermoplastic resin containing a compound represented by the formula (Y, R, R' are each a 1-10C alkyl, alkenyl, or aralkyl, a halogen, where R and R' is chlorine, when they each represent a halogen), typically 2-methyl-4- isothiazolin-3-one, 2-methyl-5-chloro-4-isothiazolin-3-one, 1,2-benzoisothiazolin-3- one, their metal salt or amine salt complex. In a preferred embodiment, the coating thermoplastic resin has a melting point more than 50 deg.C lower than that of the core fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a net for cultivating fish and shellfish (ikes net), which has a very small amount of aquatic organisms attached thereto even when used for long-term cultivation of seafood in seawater or freshwater.

[0002]

2. Description of the Related Art As nets used for a long period of time in seawater or freshwater, for example, fish nets for breeding fish breeding fish such as red sea bream, tiger pufferfish, flounder, hamachi, baskets for shellfish cultivation such as pearl oysters, scallops, and oysters. There is a net. While these nets and netting are in contact with seawater or freshwater, the surface of the aquatic organisms, such as algae and diatoms, algae such as sea anemones and hydroids, sponges such as sea sponge, Annelids such as the mosquitoes, tactile objects such as bryozoans, arthropods such as barnacles, protozoa such as sea squirts, and mollusks such as mussels are attached and inhabit.

[0003] Adhesion of aquatic organisms causes serious obstacles to cultured fish and shellfish, such as oxygen deficiency due to a decrease in the fluidity of seawater or freshwater, and the occurrence of parasites such as stink bugs and spider dams.

A net used in contact with seawater or freshwater has heretofore been used as a countermeasure for preventing the aquatic organisms from adhering as described above to tributyltin oxide, triphenyltin oxide, triphenyltin acetate, triphenyltin acetate and triphenyltin oxide. A method of treating a fiber constituting a net with an organotin compound such as phenyltin chloride has been widely adopted. However, the use of an organotin compound has a problem in that when treating a fiber product with the use thereof, it is accompanied by severe unpleasant odor and pungent odor, thereby deteriorating the working environment. Moreover, abnormal accumulation of organotin compounds in the body of fish and shellfish causes serious adverse effects such as malformation and death of fish and shellfish. It has recently been shown to have adverse effects.

[0005] Further, a paint containing a metal such as copper, silver, zinc, nickel or the like which has an adhesion inhibiting effect on aquatic organisms or a compound containing them, or an organic compound such as nitrogen, sulfur or halogen is used. Although there is a method of coating on the surface, the rate of dissolution into seawater or freshwater is high, and as a result, cultured fish and shellfish may die, and they cannot be used particularly for nets for culturing fry and shellfish.

Therefore, as a means for preventing such a serious adverse effect, it is necessary to replace the nets and cages every week to clean and repair the nets to which the organisms have adhered.
A great deal of effort and time has been spent on the work.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the necessity of coating with a paint, and to provide high safety to seafood and human bodies,
It is an object of the present invention to provide a fish and shellfish cultivation net (ikes net) which is durable and can prevent the attachment of aquatic organisms for a long time.

[0008]

An object of the present invention is to provide a coated yarn which is coated with a thermoplastic resin containing a compound represented by the following general formula (1), a metal salt thereof, or an amine salt complex. This is achieved by providing a fish network for fish culture.

[0009]

Embedded image

As the compound represented by the general formula (1),
It is an organic nitrogen-sulfur compound, and the alkyl group, alkenyl group, and aralkyl group represented by Y, R, and R ′ are each preferably a group having 1 to 10 carbon atoms, and as a halogen atom represented by R and R ′ Is preferably chlorine.

A specific example of the compound is 2-methyl-4-
Isothiazolin-3-one, 2-methyl-5-chloro-
4-isothiazolin-3-one, 1,2-benzoisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazoline-3 -On and the like. These compounds are zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc acetate, copper chloride, copper bromide, copper nitrate, nickel chloride, calcium chloride, magnesium chloride, iron chloride, manganese chloride, sodium chloride, chloride It may be combined with a metal salt such as barium or an amine salt such as ammonium chloride or another amine chloride to form a complex compound.

The content of the compound in the thermoplastic resin is 0.1 to 10% by weight in consideration of the effect of preventing aquatic organisms from adhering.
Is preferably within the range. The effect is not improved even if the content is increased, and the effect is not exhibited if the content is too small. A more preferred content is in the range of 3-7% by weight.

The thermoplastic resin containing the above-mentioned compound is a diol-modified polyester, which is a point of heat fusion utilizing a melting point or a softening point difference with a polymer forming a core yarn to be described later. It is preferable from the viewpoint of kneading with the compound. Polyester is polyethylene terephthalate
And general-purpose polyesters such as polybutylene terephthalate. Polyhexamethylene terephthalate consisting of terephthalic acid and 1,6-hexanediol can be used.
It is preferable to use the heat-sealing property, the melting point, and the workability such as fiber strength. Geo- which can modify the polyester
Ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol
, Cyclohexane-1,4-dimethanol, polyethylene glycol, polytetramethylene glycol, and the like. The modification rate is not particularly limited, but considering the handling properties such as melting point and melt viscosity, ethylene glycol -Diethylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexane-1,4-dimetanol
Are 10 to 10 of the diol components constituting the polyester.
The content is preferably in the range of 50 mol%, and the content of polyethylene glycol, polytetramethylene glycol, etc. is preferably in the range of 1 to 20% by weight of the diol component constituting the polyester.

The diol modified polyester has a melting point of 150 ° C. or less and a melt viscosity of 10,000 poise or less (16
0 ° C, capillary length 10 mm, capillary diameter 1 m
m, and a shear rate of 1,000 sec ^-1 ). When the melting point exceeds 150 ° C., it is necessary to apply heat exceeding 180 ° C. in each step of kneading, spinning, and molding with the above-mentioned compound by heat melting, and the above-mentioned compound is vaporized or decomposed, and its effect is reduced. It may decrease. If the melt viscosity is too high, shear heat insulation of 180 ° C. or more occurs in each of the kneading, spinning, and molding steps, which may cause vaporization and decomposition of the above-mentioned compounds. More preferred melting point is 14
At 0 ° C. or lower, the melt viscosity ranges from 2000 to 5000 poise.

Some of the diol modified polyesters have a high melting point. In this case, it is preferable to add a melting point depressant to lower the melting point. Medium molecular polymers such as polybutene and liquid polyester can be used as melting point depressants. The melting point is 150 ° C.
The amount is not particularly limited as long as it is added in such an amount that the melt viscosity decreases to below, and the melt viscosity decreases to 10,000 poise or less.

Further, in the above-mentioned diol modified polyester, a modifier such as a conductivity improver and an ultraviolet absorber, and an additive such as a coloring pigment can be appropriately contained.

The polymer forming the core yarn coated with the above-mentioned thermoplastic resin is preferably a polymer whose melting point or softening point is at least 50 ° C. higher than the melting point or softening point of the thermoplastic resin. The polymer is not particularly limited as long as it is a polymer having a softening point. However, it is preferable that the coating made of the thermoplastic resin does not peel off from the core yarn and that the coating yarn retains the strength. In the present invention, in order to improve the process passability of a rapier loom described below, it is desirable that the coating resin and the core yarn are bonded so as not to cause coating peeling. It is desirable that there is no gap between the core yarn. If the melting point or softening point difference is less than 50 ° C., fusing and remarkable shrinkage occur at the time of melt extrusion coating and thermal fusion at the intersection of the warp and weft, which will be described later, making processing impossible.

The above-mentioned modified diol is used as a thermoplastic resin, and a saturated polyester such as polyethylene terephthalate and polybutylene terephthalate, a polyarylate,
It is preferable that the core yarn is formed of a wholly aromatic polyester, a wholly aromatic aramid or the like.

There is also a coating method in which the above-mentioned thermoplastic resin is dissolved in a solvent and applied to the surface of the core yarn.
It is preferable to coat the core yarn by a melt extrusion method.

Regarding the core yarn, irrespective of the form of the filament yarn or spun yarn, a ply-twisted yarn or the like made of these can be used according to the purpose. The filament yarn may be a monofilament or a multifilament.

The method for producing a net according to the present invention is not particularly limited as long as it is a method capable of producing a net in which a coated yarn obtained by coating a core yarn with a thermoplastic resin containing the above-mentioned compound forms a Moji-mesh. There is no restriction. An example of the manufacturing method will be described. First, using a twin-screw kneader, the above compound, and other compounds, and the thermoplastic resin are uniformly mixed by a twin-screw kneading extruder, guided to a die shown in FIG. 1, and coated on the surface of the core yarn. . In order to enhance the adhesiveness between the coating resin and the core yarn, it is preferable to use the pressurized die shown in FIG. By making the difference between the melting point or softening point of the polymer forming the core yarn and the thermoplastic resin containing the above-mentioned compound 50 ° C. or more, the heat is almost uniformly applied to the surface of the core yarn having a soft and uneven cross section. Possible plastic resin can be coated. In addition, it is possible to suppress single yarn breakage due to excessive deformation and friction applied to the core yarn softened by contact with the coating resin.

The traveling speed and draft rate of the core yarn can be appropriately set, and the coated yarn that has been drafted is guided to a cooling zone shown in FIG. 2, cooled, solidified, and wound up.
At the time of this winding, the covering yarn may be flattened by receiving a pressure that causes plastic deformation. Next, a mesh is formed by entangled weaving using a rapier loom or the like using the obtained coated yarn. At this time, the wefts form the Megori eyes.
Then, a net can be obtained by heat-sealing the intersections of the warp and the weft by dry heating. By heat-sealing the intersection of the warp and weft, misalignment can be prevented,
It can be used as a net.

At first glance, the net of the present invention is a net having a square mesh, in which wefts are interwoven with warps like a woven fabric.
It can be used mainly in the field of fine netting, such as iriko patch nets, fry of yellowtail, red sea bream, flounder, tiger puffer, etc., cultivation nets (fish cage nets), laver nets, seaweed cultivation, pearl oysters,
It is useful for scallops, oysters, and other farming cages.

[0024]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The physical property values in the examples are values measured by the following methods. (1) Criteria for determination of aquatic organism attachment status 5: No attachment of organisms was observed. 4: Adherence of organisms was observed on about 10% of the entire surface of the object. 3: Adhesion of organisms was observed on about 20% of the entire surface of the object. 2: About 50% of the entire surface of the target object was found to have attached organisms. 1: Adhesion of organisms was observed on the entire surface of the object. (2) Melting point (° C.) of polymer Differential scanning calorimeter (TC processor-TC manufactured by Metra Corporation)
10A). (3) Melt viscosity (poise) of polymer Capillograph (Capillograph 1C, manufactured by Toyo Seiki Co., Ltd.)
Was used to measure the melt viscosity at 160 ° C.

Example 1 1,4-butanediol 30 mol% modified polyhexamethylene terephthalate [Intrinsic viscosity: 0.86 (measured in a mixed solvent of phenol / tetrachloroethane and the like at 30 ° C.)] Melting point: 126 ° C., melt viscosity: 4000 poise]
FIG. 1 contains 6% by weight of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 6% by weight of polybutene having an average molecular weight of 3000 (2000H, manufactured by Idemitsu Petrochemical Co., Ltd.). Using a pressing die shown in (a) and an apparatus shown in FIG. 2, a polyarylate multifilament (made by Kuraray: melting point: 320 ° C., 1000 denier / 200 filament, 80 T / M single twist) 100
The resin was coated with 200 parts by weight to obtain a resin-coated yarn. Next, a warp density of 4 × 2 / inch and a weft density of 4 × 2 /
An woven mesh of inches (meaning that two coated yarns are present in one inch) was prepared and heated at 151 ° C. for 30 seconds to thermally fuse the intersections of the warp and the weft to obtain a net. This net is 3
It is immersed in the sea (the Seto Inland Sea) for a year to observe the state of attachment of aquatic organisms, and the results are shown in Table 1. No adhesion of aquatic organisms was observed at all even after immersion in the sea for 3 years.

Example 2 The procedure of Example 1 was repeated except that the ethylene glycol 20 mol% modified polyhexamethylene terephthalate (melting point: 137 ° C.,
Melt viscosity: 3300 poise), except that 100 parts by weight of polyarylate multifilament is coated with 200 parts by weight of the coating resin, and the resulting coated yarn is used to form a woven net of entangled weave. Was prepared. Then 1
The woven net was heated at 62 ° C. for 30 seconds, and the intersections of the warp and the weft were heat-sealed to obtain a net. This net was immersed in the sea for three years, and the state of attachment of aquatic organisms was observed. Table 1 shows the results. No adhesion of aquatic organisms was observed even after immersion in the sea for 3 years.

Example 3 A polyarylate multifilament 100 was prepared in the same manner as in Example 1 except that 10 mol% of isophthalic acid-modified polyhexamethylene terephthalate (melting point: 135 ° C., melt viscosity: 3,500 poise) was used. By weight, the coating resin was coated so as to be 200 parts by weight, and a woven net of entangled weaving was produced using the obtained coated yarn. Then 160 ° C
For 30 seconds to heat-bond the intersections of the warp and the weft to obtain a net. Soak this net in the sea for three years,
The state of attachment of aquatic organisms was observed. Table 1 shows the results. 3
No aquatic organisms adhered when immersed in the sea for a year.

Example 4 In Example 1, an aramid multifilament (Kevlar, manufactured by DuPont, melting point: 560 ° C., 40) was used as the core yarn.
0 denier / 267 filament, 80T / M single twist) in the same manner as above.
Parts by weight of the coating resin is coated so as to be 200 parts by weight,
Using the obtained coated yarn, a woven net of entangled weave was prepared (warp density: 4 × 4 / inch, weft density: 4 × 4 / inch). Then, the woven mesh was heated at 125 ° C. for 90 seconds,
The intersection of the warp and the weft was heat-sealed to obtain a net. However,
Although the adhesiveness between the core yarn and the coating resin was slightly peeled as compared with the coated yarn obtained in Example 1, there was no practical problem. This net was immersed in the sea for three years, and the state of attachment of aquatic organisms was observed. Table 1 shows the results. No adhesion of aquatic organisms was observed even after immersion in the sea for 3 years.

Example 5 Example 1 was repeated except that polyethylene terephthalate multifilament (Kraftel, Kuraray, melting point: 273 ° C., 1000 denier / 192 filament, 80 T / M single twist) was used as the core yarn. In the same manner, 100 parts by weight of the multifilament was coated with 200 parts by weight of the coating resin, and a woven net of entangled fabric was prepared using the obtained coated yarn. Then, the woven mesh was heated at 125 ° C. for 90 seconds to thermally fuse the intersections of the warp and the weft,
Got the net. This net was immersed in the sea for three years, and the state of attachment of aquatic organisms was observed. Table 1 shows the results. No adhesion of aquatic organisms was observed even after immersion in the sea for 3 years.

Comparative Example 6 Nylon 6 multifilament Mol nets for fry cultivation with a mesh size of 90 were immersed in the sea to observe the state of adhesion of aquatic organisms. In about one week, a large amount of aquatic organisms adhered to the net, clogging the eyes and making it unusable as a net.

[0031]

[Table 1]

[0032]

The net of the present invention does not adhere to aquatic organisms even when immersed in the sea for a long period of time, and is most suitable for fish and shellfish nets.
It is also useful as a seaweed net and seaweed net as well as seafood.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a main part of a molding die capable of producing a coated yarn of the present invention.

FIG. 2 shows a simplified process diagram in which the coated yarn of the present invention can be manufactured.

Claims (2)

[Claims] 1. A seafood cultivation wherein a coated yarn coated with a thermoplastic resin containing a compound represented by the following general formula (1), a metal salt thereof or an amine salt complex forms a Mogi group. network. Embedded image 2. The thermoplastic resin has a melting point or softening point of 5 from the melting point or softening point of the polymer forming the core yarn of the coated yarn.
The fish and shellfish cultivation net according to claim 1, wherein the temperature is lower than 0 ° C.