JPH0748744A - Antifouling composite yarn and antifouling material using this antifouling composite yarn - Google Patents

Abstract

PURPOSE:To obtain an antifouling composite yarn capable of satisfying problems of lasting property of antifouling effect, productivity and production cost without inconsistency and an antifouling material such as a rope or fishing net, etc., using this yarn. CONSTITUTION:This antifouling composite yarn is obtained by covering at least surface of monofilament or its twist yarn with flat yarn obtained from a thermoplastic resin composition containing copper or a copper compound and a water-soluble resin. Antifouling material of a rope, a net body, etc., is constituted of this antifouling composite yarn.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a safe and inexpensive antifouling composite yarn which is resistant to pollution by aquatic organisms such as barnacles and sea lions and other algae, molds, bacteria and the like, and an antifouling product using the same. Regarding materials

[0002]

2. Description of the Related Art In recent years, the cultivation and fishing industry has become popular, and a large amount of nets, ropes, floats, etc. are used in aquaculture facilities. In such aquaculture facilities, fishing nets, ropes, floats, etc. are soaked in seawater for a long period of time, while aquatic organisms such as barnacles and sea lions adhere to the fishing nets, ropes, floats, etc. that compose them. , Block the mesh or reduce the buoyancy of the float. Particularly in pearl culture, when barnacles, sea lions, etc. adhere to the ropes and nets, they themselves become heavy, and as a result, the pearls suspended on the ropes and nets sink downward and fall into an oxygen deficient state, resulting in poor growth. For this reason, it is necessary to frequently remove aquatic organisms attached to ropes and nets, but this is a time-consuming and difficult task.

Similarly, in fish culture and the like, the attached aquatic organisms cause the ropes, nets, and the like to sink, which increases the number of fish lost, and the habit of rubbing fish bodies against the nets to scrape off parasites. In aquaculture of yellowtail, yellowtail, etc.,
The barnacles and the like attached to the outer skin damage the commercial value and reduce the commercial value, and there is a great risk of mortality due to invasion of pathogenic bacteria from this part, which causes a great deal of damage to the trader.

Therefore, conventionally, fishing nets and ropes have been immersed in an antifouling treatment agent containing a copper compound, an organic compound or the like to prevent adhesion of aquatic organisms. However, since the antifouling effect by such an antifouling agent lasts only for about 1-2 months at the best, the traders are forced to disinfect the ropes and nets and to perform the antifouling treatment.

On the other hand, instead of applying copper or a copper compound having a repellent effect on aquatic organisms, a wire or a rope made of powdery solid copper, that is, a polyethylene monofilament is coated with copper wire. A twisted rope, a rope made of polyethylene monofilament kneaded with metal copper powder, a rope made of polyethylene monofilament containing a water-absorbent resin kneaded with metal copper powder, and the like have been proposed and used.

However, the above is not effective unless the amount of copper wire is large, and the above is the period of existence of the copper powder deposited on the surface of the monofilament (usually 1
It is effective only for about a year), and the above has the problem that the strength of the rope itself decreases. In addition, both of them have the drawback that the metallic copper changes into a stable compound of copper oxide or copper carbonate, and the antifouling effect does not last for two years. Also, the copper powder itself is more expensive than, for example, polyethylene, so the price of the rope itself is lower than that of ordinary polyethylene.
The price will be 2.5 to 6 times higher.

[0007]

Therefore, the problem to be solved by the present invention is to use an antifouling composite yarn and this yarn which satisfy the problems of sustainability of antifouling effect, productivity, production cost, etc. without contradiction. It is to provide antifouling materials such as ropes and fishing nets.

[0008]

Thus, according to the invention of "Claim 1" of the present application, "a monofilament in a flat yarn obtained from a thermoplastic resin composition containing copper or a copper compound and a water-soluble resin" Alternatively, an antifouling composite yarn ”is provided which is obtained by coating at least the surface of the twisted yarn.

The copper or copper compound in the present invention is used as an antifouling active ingredient. Examples of the copper compound include cuprous oxide, copper chloride, and copper sulfate.
Cuprous oxide is preferred. Since this cuprous oxide gradually changes to black copper oxide in moist air, it is preferably stored in dry air or in an inert gas atmosphere before use. Both copper and copper compounds are used in powder form.
The particle size of these is preferably about 1 to 30 μm.

As the water-soluble resin used in the present invention,
Examples thereof include polyethylene oxide and polyvinyl alcohol, with polyethylene oxide being preferred. The polyethylene oxide is a white powder obtained by ring-opening polymerization of ethylene oxide, which can be used with an average molecular weight of 1,000 to several millions, but dispersibility in a base thermoplastic resin described later, mixing Considering the influence on strength and water solubility, the average molecular weight is preferably 2,000,000 or less, more preferably about 10,000 to 500,000. The polyethylene oxide referred to in the present invention is a concept including not only a homopolymer of ethylene oxide but also a random or block or graft copolymer of ethylene oxide and propylene oxide or butylene oxide and other alkylene oxides. These other alkylene oxides may be used alone or in combination of two or more.

Examples of the thermoplastic resin used in the present invention include polyethylene, polypropylene, polyamide, polyvinylidene chloride, polyvinyl chloride, polyester, ethylene / propylene rubber, ethylene / vinyl acetate copolymer, and thermoplastic polyurethane elastomer. Although known thermoplastic resins or thermoplastic elastomers are included, considering mainly the fishing nets that are most in demand, polyolefin resins are advantageous in view of price, miscibility with water-soluble resins, and the like. Two or more thermoplastic resins may be mixed if desired.

The thermoplastic resin composition of the present invention is obtained by mixing the above water-soluble resin in the above thermoplastic resin in a predetermined ratio, and then adding copper or a copper compound in a predetermined ratio. In the above composition, the copper or copper compound is 5 to
It is used in the range of 35% by weight, preferably 10 to 25% by weight.
In the above composition, the water-soluble resin is used in the range of 1 to 10% by weight.

The thermoplastic resin composition may contain, if desired, known substances such as a foaming agent, an ultraviolet absorber, an antistatic agent, an antiaging agent, a weathering agent, a lubricant, an inorganic filler, a bactericide and an antifungal agent. Agents, colorants, etc. may be added. Further, when a rubber material such as EP rubber or EPDM is used, rubber components such as a vulcanizing agent, a vulcanization accelerator, a process oil, and zinc white may be appropriately added.

The flat yarn in the present invention is obtained by subjecting the above-mentioned thermoplastic resin composition to a known method such as, for example, once molding it into a pellet form, film-forming it from this, and stretching the film. You can The flat yarn used in the present invention preferably has a denier of 500 to 2000, but is not limited thereto.

As the monofilament or the twisted yarn thereof used in the present invention, those known in the art can be used as they are. In the case of twisted yarn, it may be composed of monofilaments of the same kind. Further, it may be composed of two or more kinds of monofilaments.

In the present invention, the monofilament or the twisted yarn thereof is coated with the flat yarn. In this case, the flat yarn and the monofilament or the twisted yarn may be twisted together, and the surface of the monofilament or the twisted yarn may be flat yarn. May be wrapped around. In any case, it is necessary that at least the surface of the monofilament or its twisted yarn is covered with a flat yarn.

As the monofilament or the twisted yarn thereof to be covered with the flat yarn, those known in the art can be used as they are, and those composed of high density polyethylene (HDPE) and the like can be mentioned as preferable ones.

In the antifouling composite yarn of the present invention, the antifouling active ingredient is gradually ionized like copper and has a specific gravity of about 2/3 of copper and a price of about 1/4 of copper. The cuprous oxide is preferably selected. Polyethylene oxide is preferable as the water-soluble resin. Therefore, by selecting these, at least the surface of the monofilament or its twisted yarn in the flat yarn obtained from the "thermoplastic resin composition containing cuprous oxide and polyethylene oxide" as shown in "Claim 2" of the present application. Can be provided.

The present invention can also provide the invention according to the "claim 3" or "claim 4" of the present application. That is, by coexisting a metal or a compound thereof having a higher ionization tendency than copper to copper or a copper compound which is the antifouling active ingredient in the present invention, a local battery is formed to mitigate the oxidation of copper or the copper compound. At the same time, since the flat yarn can be made porous by being ionized and eluted earlier than copper or the copper compound, the duration and efficiency of the antifouling active ingredient can be improved.

From the viewpoints of safety, stability, price, etc., as the metal or its compound having a higher ionization tendency than copper, calcium oxide, zinc, zinc oxide, magnesium,
Magnesium oxide, aluminum, aluminum oxide,
Iron and iron oxides (II and III) are preferable, and ferric oxide (Fe ₂ O ₃ ) called red iron oxide is particularly preferable because it is inexpensive and its color tone is similar to cuprous oxide. The metal or compound thereof having a higher ionization tendency than copper is usually used in a particle size smaller than that of the antifouling active ingredient.

Further, the present invention can provide an antifouling material using the above antifouling composite yarn. For example, the invention according to "Claim 5" of the present application provides an antifouling rope, and the invention according to "Claim 6" of the present application provides an antifouling net.

[0022]

According to the invention of "Claim 1" of the present application, at least the surface of the monofilament or its twisted yarn is coated with a flat yarn obtained from a thermoplastic resin composition containing copper or a copper compound and a water-soluble resin. Therefore, in water, first, the copper or the copper compound existing on the surface of the flat yarn is eluted into the water to exhibit the antifouling effect. After a lapse of a predetermined time, the water-soluble resin existing on the surface of the flat yarn gradually dissolves in water, and cracks and micropores are formed in the traces, and water penetrates into these cracks and micropores and copper or copper in the vicinity thereof is formed. The copper compound is eluted and the antifouling effect is maintained. Since aquatic organisms are repelled in the vicinity where the antifouling component is eluted, the aquatic organisms do not adhere to the monofilaments and their strands coated on the flat yarn. Further, since cracks and fine pores are generated by elution of the water-soluble resin only in the flat yarn on the surface, the internal monofilament and its strand are not affected and the strength is maintained. Furthermore, since it is wider than the monofilament if configured into a flat yarn, it is possible to use copper or a copper compound having a relatively large particle size,
Even if these are contained, the notch effect is small, yarn breakage is unlikely to occur, and durability is imparted.

According to the invention of "Claim 2" of the present application,
Polyethylene oxide has good miscibility with the base resin,
Since the yarn is not broken during drawing during the production of the flat yarn, and the flat yarn is uniformly dispersed in the obtained flat yarn, the antifouling component elution effect is uniform in the entire flat yarn. Further, cuprous oxide has a smaller specific gravity than copper powder and gradually ionizes like copper, so that the weight can be reduced and the antifouling effect can be endured.

According to the invention of "Claim 3" of the present application,
Since copper or a copper compound and a metal or a compound thereof having a higher ionization tendency than copper coexist in the flat yarn, a metal or a compound thereof having a higher ionization tendency than copper is easily eluted in the flat yarn by the action of a local battery. However, this and the elution of the water-soluble resin are overlapped to promote the generation of cracks and fine pores in the flat yarn, and as a result, the elution of the antifouling active ingredient is promoted.

According to the invention of "Claim 4" of the present application,
Since iron or its compound coexists with copper or a copper compound in the flat yarn, the antifouling composite yarn in which the elution of the antifouling active ingredient is promoted by the action of the local battery can be provided at low cost.

According to the invention of "Claim 5" of the present application,
Since the rope is composed of an antifouling composite yarn whose surface is coated with a flat yarn containing an elutable antifouling active ingredient, the entire surface of the rope is antifouling treated and the strength is that of a normal rope. Is equivalent to.

According to the invention of "Claim 6" of the present application,
Since the net body is composed of the antifouling composite yarn whose surface is covered with the flat yarn containing the antifouling active ingredient that can be eluted, the surface of the net body is all antifouling treated and the strength is usually It will be equivalent to the rope.

[0028]

The present invention will be described in detail below with reference to the illustrated embodiments, but the present invention is not limited thereto. Example 1 [Fabrication of Flat Yarn] A thermoplastic resin composition having the following composition was prepared, which was kneaded with a kneader and molded into pellets with a square pelletizer. HDPE 69% by weight Polyethylene oxide (average molecular weight: about 500,000) 6% by weight Cuprous oxide (average particle size: about 2 μm) 20% by weight Iron oxide powder (average particle size: about 1 μm) 5% by weight The above pellets are heated to 180 ° C. Film (thickness 150
μm), and this film was dry-stretched (8-fold stretched) on a rotating roll at 100 ° C. to obtain a flat yarn (900 ^D ) having a width of 3 mm.

[Preparation of Antifouling Composite Yarn] The flat yarn (900 ^D ) is twisted at a ratio of 8 polyethylene monofilaments (400 ^D ), and the surface is completely covered with the flat yarn at this time. Thus, an antifouling composite yarn was produced.

[Preparation of Antifouling Material] Next, 120 pieces of the above-mentioned antifouling composite yarn are twisted together to form an antifouling strand, and further three strands are twisted together to obtain 22 mmφ
The rope of The tensile strength of the above rope is 5000kg
Then, a similar process was performed using only HDPE monofilament 22
No reduction in strength was observed for the 5050 kg tensile strength of the mmφ rope. When the antifouling effect was observed while the above antifouling rope was immersed in seawater for about 2 years, no adhesion of aquatic organisms such as barnacles was observed on the surface of the rope.

Example 2 [Preparation of flat yarn] A thermoplastic resin composition having the following composition was prepared, which was kneaded with a kneader and molded into pellets with a square pelletizer. HDPE 82% by weight Polyethylene oxide (average molecular weight: about 20,000) 3% by weight Copper sulfate (average particle size: about 30 μm) 10% by weight Zinc powder (average particle size: about 1 μm) 5% by weight After drying for an hour, a film (thickness 150 μm) is produced with an extruder at 180 ° C.
Dry stretching (8 times stretching) was performed on a rotating roll at 100 ° C. to obtain a flat yarn (800 ^D ) having a width of 4 mm.

[Preparation of Antifouling Composite Yarn] The flat yarn (800 ^D ) is twisted at a ratio of 12 polyethylene monofilaments (400 ^D ), and the surface is completely covered with the flat yarn. Thus, an antifouling composite yarn was produced.

[Preparation of Antifouling Material] Next, 10 antifouling composite yarns were twisted together to produce an antifouling strand, and further 3 strands were twisted together to prepare a 6 mmφ rope. The tensile strength of the above rope is 370kg, HD
No decrease in strength was observed with respect to a tensile strength of 370 kg of a 6 mmφ rope produced in the same manner using only PE monofilament. When the antifouling effect was observed while the above antifouling rope was immersed in seawater for about 2 years, no adhesion of aquatic organisms such as barnacles was observed on the surface of the rope.

Example 3 [Production of Flat Yarn] A thermoplastic resin composition having the following composition was prepared, which was kneaded with a kneader and molded into pellets with a square pelletizer. HDPE 69% by weight Polyethylene oxide (average molecular weight: about 500,000) 6% by weight Cuprous oxide (average particle size: about 2 μm) 20% by weight Iron oxide (average particle size: about 1 μm) 5% by weight The above pellets were used in Example 2 A flat yarn (800 ^D ) having a width of 4 mm was obtained in the same manner as in.

[Preparation of Antifouling Composite Yarn] The flat yarn (800 ^D ) is wound on the monofilament by winding it with a ring type twisting machine at a ratio of 8 polyethylene monofilaments (400 ^D ) to the antifouling property. A composite yarn was made.

[Preparation of Antifouling Material] Next, the above 12 antifouling composite yarns were twisted together with a twister to prepare an antifouling strand, and these 3 strands were twisted together to form 6
A rope of mmφ was prepared. The surface of the antifouling rope was almost completely covered with a flat yarn, and when the antifouling effect was observed by immersing the rope in seawater, the antifouling effect for two years or more was observed.

Example 4 [Production of Flat Yarn] A thermoplastic resin composition having the following composition was prepared, which was kneaded with a kneader and molded into pellets with a square pelletizer. HDPE 67% by weight Polyethylene oxide (average molecular weight: about 500,000) 3% by weight Electrolytic copper powder (average particle size: about 30 μm) 25% by weight Zinc powder (average particle size: about 3 μm) 5% by weight The above pellets were used in Example 2 A flat yarn (800 ^D ) having a width of 4 mm was obtained in the same manner as in.

[Preparation of Antifouling Composite Yarn] A flat yarn (800 ^D ) was wound on the monofilament with a ring type twisting machine at a ratio of 8 polyethylene monofilaments (400 ^D ) to the monofilament and the antifouling property was obtained. A composite yarn was made.

[Preparation of Antifouling Material] Next, the above 12 antifouling composite yarns were twisted together with a twister to prepare an antifouling strand, and these 3 strands were twisted together to form 6
A rope of mmφ was prepared. The surface of the antifouling rope was almost completely covered with a flat yarn, and when the antifouling effect was observed by immersing the rope in seawater, the antifouling effect for two years or more was observed.

Example 5 [Preparation of flat yarn] A thermoplastic resin composition having the following composition was prepared, which was kneaded with a kneader and molded into pellets with a square pelletizer. Polypropylene 70% by weight Polyvinyl alcohol (polymerization degree 1500) 5% by weight Cuprous oxide (average particle size: about 2 μm) 20% by weight Iron oxide (average particle size: about 1 μm) 5% by weight The above pellets are dried at 90 ° C. for 4 hours. Then, a film (thickness 150 μm) is produced with an extruder at 180 ° C, and this film is
Dry stretching (8 times stretching) was performed on a rotating roll at 100 ° C. to obtain a flat yarn (800 ^D ) having a width of 4 mm.

[Preparation of Antifouling Composite Yarn] One flat yarn (800 ^D ) was twisted with 12 polypropylene monofilaments (400 ^D ), and the surface was completely covered with the flat yarn. Thus, an antifouling composite yarn was produced.

[Preparation of Antifouling Material] Next, 10 antifouling composite yarns were twisted together to prepare an antifouling strand, and further 3 strands were twisted together to prepare a 6 mmφ rope. The tensile strength of the above antifouling rope is 380Kg
So, it was made from polypropylene monofilament only 6
No reduction in strength was observed with respect to the tensile strength of the mmφ rope. When the antifouling effect was observed while the above antifouling rope was immersed in seawater for about 2 years, no adhesion of aquatic organisms such as barnacles was observed on the surface of the rope.

Comparative Example 1 The same thermoplastic composition as in Example 3 was used to prepare a direct soil resistant monofilament (400 ^D ) without forming a flat yarn. An antifouling composite yarn was prepared by twisting two antifouling monofilaments (400 ^D ) at a ratio of 8 HDPE monofilaments (400 ^D ) to prepare a 6 mmφ rope in the same manner as in Example 3. It was made. The surface of the rope could not be completely covered with the antifouling monofilament, and when immersed in seawater, the antifouling effect was short, being 3 to 4 months.

Comparative Example 2 An attempt was made to produce an antifouling monofilament (800 ^D ) with the same thermoplastic composition as in Example 4, but the stretch breakage occurred frequently and the monofilament could not be obtained. It is considered that this is because the notch effect worked greatly because the particle size of the electrolytic copper powder was large.

[0045]

As described above, according to the present invention,
Since the surface is completely covered with the antifouling flat yarn, it is possible to provide an antifouling composite yarn having a continuous antifouling effect. Further, since the inside is made of a normal monofilament or its twisted yarn, the strength is not reduced as compared with the antifouling material constituted by only this monofilament. Therefore, it is possible to provide an excellent antifouling composite yarn satisfying the problems such as sustainability of the antifouling effect and productivity without contradiction and an excellent antifouling material such as ropes and fishing nets using the yarn at low cost. Furthermore, since the composition containing copper or a copper compound as an antifouling active ingredient is wider than the monofilament called flat yarn, the notch effect can be suppressed even if copper or a copper compound having a large particle size is contained. Can
The antifouling effect can be further maintained while maintaining the strength.

Claims (6)

[Claims] 1. An antifouling composite yarn obtained by coating at least the surface of a monofilament or a twisted yarn thereof with a flat yarn obtained from a thermoplastic resin composition containing copper or a copper compound and a water-soluble resin. 2. An antifouling composite yarn obtained by coating at least the surface of a monofilament or a twisted yarn thereof with a flat yarn obtained from a thermoplastic resin composition containing cuprous oxide and polyethylene oxide. 3. The antifouling composite yarn according to claim 1, wherein the thermoplastic resin composition contains a metal having a higher ionization tendency than copper or a compound thereof. 4. The antifouling composite yarn according to claim 3, wherein the metal having a higher ionization tendency than copper is iron. 5. An antifouling material comprising a rope made of the antifouling composite yarn according to any one of claims 1 to 4. 6. An antifouling material comprising a net body made of the antifouling composite yarn according to any one of claims 1 to 4.