JPH06145017A - Antifouling material composition and antifouling product - Google Patents

Abstract

PURPOSE:To obtain a lightweight antifouling composition having persistence for a long period without using expensive copper powder and a synthetic resin molded product utilizing the antifouling composition. CONSTITUTION:This antifouling composition is a thermoplastic synthetic resin composition comprising polyethylene oxide and cuprous oxide, preferably further a metal or its oxide having a higher ionization tendency than that of the copper. Although the elution rate of the copper ions can be regulated by the amount of the added polyethylene oxide, it is further increased by the coexistence of the metal or its oxide having the higher ionization tendency than that of the copper (preferably iron sesquioxide). This synthetic resin molded product is used as crawls or set nets, constituting materials or lining materials for ropes, floats or water tanks for culturing, wall materials for bathrooms, refuse containers or drainings for kitchens, drain pipes, constituent materials or lining materials for mooring materials such as buoys or marker buoys, lining materials for conduit pipes for hydraulic power plants, lining material substitutes for ship bottom coating materials and other uses.

Description

Detailed Description of the Invention

[0001]

[Object of the Invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a safe antifouling material composition resistant to contamination by aquatic organisms, algae, molds, bacteria and the like, and an antifouling product using the composition.

[0002]

[Prior art]

(1) Background of the Invention In recent years, the cultivation and fishing industry has become popular, and a large amount of nets, ropes, floats, etc. are used for aquaculture cages. In this aquaculture facility, fish nets, ropes, floats, etc. are immersed in seawater for a long period of time, while aquatic organisms such as magpie, diatoms, mussels, barnacles, etc. It adheres and blocks the mesh and reduces the buoyancy of the float. In particular, the blockage of the mesh hinders the inflow of fresh seawater and causes an oxygen deficiency, which reduces the growth of cultured fish and the resistance to pests and diseases, and at the same time causes a great deal of damage to the operators due to the increase of fish lost due to the sinking of the net. give. In aquaculture of yellowtail, yellowtail, etc., there is a habit of rubbing the fish body against the net to scrape off the parasites, but the barnacles attached at that time damage the outer skin and cause the invasion of pathogenic bacteria from the part. The risk of death is also great. Similarly, in the fixed net, the attachment of aquatic organisms makes it difficult to pull up and net the net due to the increase in water flow resistance and the increase in weight.

Therefore, conventionally, fishing nets and ropes have been immersed in an antifouling treatment agent containing a copper compound, an organic tin compound or the like to prevent adhesion of aquatic organisms. However, since the antifouling effect of such an antifouling agent lasts only for about 1-2 months at the most, the trader is obliged to disinfect and antifoul the year-end net. Moreover, the use of organotin compounds has already been banned because of concern over chronic poisoning via the food chain.

Therefore, a net cage made of galvanized copper wire has been proposed as a constituent material of the cage. This metal net cage has a good shape-retaining property against waves, but it is not yet satisfactory in terms of antifouling property, corrosion resistance against seawater, and abrasion resistance. Moreover, since the zinc in the plating layer is eluted into seawater, the residual zinc in the cultured fish is more than double that of the natural fish, but this is not preferable considering the effect on the human body.

[0005] Separately, in the flounder cultivation that has recently been increasing, almost all panel water tanks on land are used. However, since vinyl sheets used as interior materials here have no antifouling property, it takes about 20 days. Then, Kagaku Hazel, diatom, barnacles, etc. adhere to the entire surface of the water tank. However, since flounder has a tendency to settle in the bottom, there is a risk that lethal pathogens will invade the cut wound due to Kazane azalea, barnacles, etc. attached to the bottom of the aquarium. Therefore, as a countermeasure,
It is necessary to remove adhered organisms about every 10 days, but not only the number of steps is required, but also fish cause stress due to migration, which may cause growth delay due to poor feeding, and eventually cause disease. , A more serious problem.
The situation is the same for a concrete water tank that replaces the panel water tank.

In view of the above-mentioned problems, recently, a net yarn in which a metal filament having a metal having a lower potential than copper (for example, Fe, Al, Zn, etc.) aligned with the copper filament is twisted with a synthetic fiber filament A fish net knitted by using (Japanese Patent Application Laid-Open No. 52-136783), a thermoplastic resin having different physical properties (for example, a thermoplastic resin having low water absorption and a thermoplastic resin having high water absorption) are mixed, and An antifouling material mixed with a metal powder having strong antifouling and bactericidal properties (JP-A-63-230771) and a fishing net rope for braiding a fine wire made of a copper alloy of a specific component and synthetic fiber (JP-A-62- 332
No. 70) is proposed.

Although the problems of pollution by aquatic organisms have been described above mainly in the fishing industry, damage by aquatic epiphytes is caused by underwater structures such as piers, piers, steel sheet piles, fenders, breakwaters, and mooring buoys. It also occurs in underwater floating materials such as, and the hull below the draft of a ship. In particular, the adhesion of marine organisms to the side of a ship causes a significant decrease in propulsion efficiency, which is a serious problem in shipping. As a simpler example, there is a garbage container in one corner of the sink, a drainage basket,
Occurrence of water stains and offensive odors caused by bacteria, mold, algae, etc. in the tableware dryer, drainage pipe, etc. is also an unpleasant phenomenon that is experienced daily.

(2) Problems of the prior art However, even with the known means described above, the sustainability of the antifouling effect,
It is not enough to satisfy the problems of productivity, production cost, etc. without contradiction. For example, Japanese Patent Laid-Open No. 63-230771 uses an antifouling material in which a small amount of polyamide 6 resin having high water absorption is mixed with a thermoplastic polyethylene resin having low water absorption, and fine copper powder is further mixed therein. A method for producing a monofilament and knitting a net by a conventional method is described. However, since the polyamide 6 itself has low water absorption and the dispersibility of the polyethylene resin is poor, the elution rate of the fine copper powder inside the monofilament is extremely slow, and therefore the antifouling ability is not sufficiently exhibited. In addition, since the miscibility between the polyethylene resin and the polyamide is poor, the latter is unevenly unevenly distributed, which reduces the strength of the fishing net. Furthermore, the methods of and are not suitable for application as an antifouling material other than the net because the method is limited to the net.

In view of the above circumstances, the applicant of the present application has previously proposed the invention according to Japanese Patent Laid-Open No. 3-56560, and has provided a novel antifouling material excellent in sustainability of antifouling effect and productivity. This antifouling material contains polyethylene oxide, a thermoplastic resin, and an antifouling metal powder (practically copper powder) as main components, and it is effective for effectively preventing the adhesion of aquatic organisms for two years or more. However, since it requires the use of expensive copper powder (market value \ 3,000 / kg), it is restricted in terms of cost performance. In addition, since the specific gravity of copper is close to 9, the weight of the entire molded product is 2.5 times or more even if it is mixed in about 20%, which also gives the user a disadvantage in terms of handling and maintenance.

[0010]

Therefore, the problem to be solved by the present invention is to solve the drawbacks of the prior art, especially the prior art of the applicant himself, and to further increase the superiority of the art. It is to provide an antifouling material.

[0011]

[Means for Solving the Problems]

(1) Concept The inventors of the present invention tried to improve the price, specific gravity, etc. of the copper powder, which had been a problem in the applicant's prior art, and as a result, tried to use cuprous oxide instead of copper powder. Even if it is possible to obtain excellent results that are not inferior to copper powder and that the use of cuprous oxide can reduce the weight of molded articles by 20% or more, and by coexisting with a metal or its oxide having a higher ionization tendency than copper. The inventors have found that the elution rate of copper ions can be further increased and have reached the present invention.

(2) Overview Based on the above findings, the present invention is an antifouling composition comprising a thermoplastic resin containing polyethylene oxide and cuprous oxide, and an antifouling composition using the composition. The main point is dirty molded products. In particular, the present invention, as a preferred embodiment, in addition to the above three components, an antifouling material composition containing a metal having a higher ionization tendency than copper or an oxide thereof, and an antifouling molded article using the composition. Include. Hereinafter, various elements constituting the invention will be described by dividing them into items.

(3) Thermoplastic resin As the thermoplastic resin usable in the present invention, for example, polyethylene, polypropylene, polyamide, polyvinylidene chloride, polyvinyl chloride, polyester, ethylene / propylene rubber, ethylene / vinyl acetate copolymer, Known thermoplastic resins such as thermoplastic polyurethane elastomers or thermoplastic elastomers are included, but considering mainly the fishnets, which have the highest demand, polyolefin resins are advantageous in consideration of price, miscibility with polyethylene oxide, etc. is there. Two or more kinds of the above thermoplastic resins may be mixed if desired.

(4) Polyethylene oxide Polyethylene oxide used in the present invention is a white powdery water-soluble thermoplastic resin which is usually obtained by ring-opening polymerization of ethylene oxide. This one has an average molecular weight of 1,00
0 to several millions can be used, but considering the dispersibility in the base thermoplastic resin, the influence on the strength during mixing, and the water solubility, the average molecular weight is 5,000 to 1,000,000, especially 10,000 to 500,000. Those in the range of are preferred.

If the average molecular weight is less than 5,000, polyethylene oxide will be dissolved out within a short period of time when processed into a fishing net, and thus no endurance effect can be expected.
If it exceeds 10,000, the dispersibility in the thermoplastic resin may be reduced and the strength of the net yarn itself may be reduced.

The term "polyethylene oxide" as used in the present invention includes 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 or other alkylene oxide. is there. These other alkylene oxides may be used alone or in combination of two or more.

The content of ethylene oxide in the thermoplastic resin is preferably 0.5% to 20%, preferably 2% to 10%. If it is less than 0.5%, the strength of the obtained film or monofilament is substantially the same as that of the control without addition, but preferable water solubility is not obtained.

(5) Cuprous oxide In the present invention, cuprous oxide (Cu ₂ O) is particularly selected as the antifouling metal oxide powder. It is to gradually ionized as with copper, specific gravity of about _^2/3 of copper, the price is about _^1/4 a being, and orange-red or tomato red and known as the copper powder It has a bright color tone, which is based on the reason that it is similar to copper red, which is a color unique to copper. Since this product is a crystalline powder belonging to the equiaxed system and gradually changes to black copper oxide (CuO) in moist air, it should be stored in dry air or in an inert gas atmosphere before use. preferable. The content of cuprous oxide in the thermoplastic resin is 10 to 30%, preferably 15 to 30%.

(6) Easy-Ionizing Additives The composition of the present invention has a relatively small amount of copper having a higher ionization tendency than copper, that is, higher than copper on the ionization column, in addition to cuprous oxide which is an antifouling main agent. It is preferable to contain a certain metal or its oxide (easily ionizable additive). Therefore, the ionization sequence; Li>K>Rb>Cs>Ra>Ba>Sr>Ca>Na>La>Ce>Mg>Sc>Pu>Th>Be>U> H
f>Al>Ti>Zr>Mn>V>Nb>B>Si>Ta>Zn>Cr>Ga>Fe>Cd>In>Tl> Co
>Ni>Mo>Sn>Ge>W>(H)> Cu > Hg ... ・ In the middle, all metals higher than copper, submetals or their oxides are suitable for the purpose, but alkali The use of metals and their oxides, some alkaline earth metals and radioactive elements, rare earth elements and their oxides is not practical in terms of stability, safety and cost. Further, it is not preferable to use metals and oxides such as zinc, tin, cadmium, lead and chromium, which have a problem of toxicity, from the viewpoint of safety.

Considering the above circumstances, calcium oxide, magnesium, magnesium oxide, aluminum, aluminum oxide, iron, and iron oxide (II and III) are considered to be suitable for the purpose, particularly called red iron oxide. Iron sesquioxide (Fe ₂ O ₃ ) is most preferable because it is cheap and its color tone is similar to cuprous oxide.

(7) Other additional components In the antifouling material of the present invention, if desired, various agents known as additives for thermoplastic resins, such as foaming agents, ultraviolet absorbers, antistatic agents, and antiaging agents. , Weathering agents, lubricants, inorganic fillers, bactericides, antifungal agents, coloring agents and the like can be added. When a rubber material such as EP rubber or EPDM is used as the synthetic resin, rubber components such as a vulcanizing agent, a vulcanization accelerator, a process oil, and zinc white are appropriately added.

(8) Shape The antifouling material of the present invention is used for molding materials such as master batches and pellets, as well as yarns such as monofilaments, cords, strands, bundles and chops, yarn secondary processing such as nets and ropes. Products, sheets, films, plate products such as plates,
It can be in the form of a mold material, pipe, foam material, injection molded product, hollow molded product, or the like.

The decrease in strength of the thermoplastic resin due to the addition of cuprous oxide, polyethylene oxide and an easily ionizable additive is relatively small. For example, the proportion of HDPE (high density polyethylene) is 25% by weight and 5% by weight, respectively. The decrease in tensile strength when adding cuprous oxide and polyethylene oxide is about 5% at best.

(9) Manufacturing Method The manufacturing method of the antifouling product of the present invention will be explained, for example, using a polyethylene resin as a base resin as an example. That is, polyethylene oxide is mixed with polyethylene resin at a predetermined ratio, and cuprous oxide and a small amount of easily ionizable additive (eg red iron oxide) are mixed at a predetermined ratio with the mixture, and the mixture is mixed with an extruder at about 180-
The mixture is heated to 250 ° C., kneaded, extruded into an arbitrary shape, cooled, cut, and molded into pellets to obtain a stain-proofing material for molding. As can be estimated from Example 1 and the attached FIG. 1, the elution rate of copper ions varies depending on the content of polyethylene oxide. Therefore, by appropriately adjusting the amount of polyethyleneoside added, the antifouling performance can be maintained. Can be adjusted freely.

The pellets are heated to 220 to 260 ° C. and kneaded, and are extruded into a shape of monofilament, multifilament, film, sheet, pipe or the like through an orifice or a die, or injection-molded or blow-molded according to each application. When it is desired to obtain a foam for a float, pellets containing a foaming agent are put into a female mold and molded into a predetermined shape by a one-stage or two-stage foaming method. Secondary processing of cords, ropes, etc. is performed according to a known method after the filament is processed into a yarn.

(10) Uses The use of the antifouling product according to the present invention includes a cage or a stationary net,
Rope, float, aquarium component material or lining material for aquaculture, bathroom wall material, kitchen garbage container or drainer, drainage pipe, buoy, tie-up component material or lining material, hull It is any object that is easily contaminated by aquatic organisms, algae, molds, bacteria, etc., as well as lining materials under the water surface, lining materials for water power transmission pipes, etc. In particular, an antifouling sheet consisting of a rubbery foam layer and a rubbery non-foaming layer containing an antifouling agent such as cuprous oxide is a lining agent that replaces antifouling paints for ships, and is not limited to simply preventing pollution. , It is useful not only for general ships and boats but also for military ships such as submarines, because it reduces wave-making resistance and exhibits ultrasonic absorption. Furthermore, it is also useful as a lining material for water pipes and irrigation canals for hydroelectric power stations suffering from the damage of flying squirrels.

[0027]

The antifouling material according to the present invention contains water-soluble polyethylene oxide as a uniform dispersion in the base resin, and cracks and fine pores are formed in the traces of the water-soluble polyethylene oxide which are gradually eluted in water. As a result of moisture invading through the cracks and micropores of the copper, the cuprous oxide powder in the core is effectively ionized and exerts its effect for a long time. However, since the micropores and cracks generated by the elution of polyethylene oxide have a microscopic size, the strength reduction due to the micropores and cracks is relatively small as described above. Moreover, because the miscibility of the base resin and polyethylene oxide is good, a molded product with uniform strength can be obtained. Especially when the object is a yarn, there is no concern that yarn breakage will occur during drawing. Bring great benefits.

In the above, a metal or its oxide having a higher ionization tendency than copper in the composition (easily ionizable additive)
The coexistence of the above causes the easily ionizable additive to dissolve due to the cell action, promotes the formation of fine pores and fine cracks, and eventually increases the elution rate of copper ions. The cuprous oxide, which is the main agent for antifouling in the composition of the present invention, has a specific gravity of about ² / of copper.
It is _3, since the price manner close to about _^1/4 of copper is also advantageous in use and manufacturing both sides.

[0029]

The embodiments of the present invention will be described below with reference to Examples and Comparative Examples, but the examples are merely for the purpose of explanation, and do not imply any limitation or limitation of the inventive idea.

Examples 1 to 3 and Comparative Example 1 Four kinds of plate-like samples (surface area 160 cm ² ) having the compositions shown in Table 1 below were prepared and immersed in a 9.8% sulfuric acid solution (liquid volume 400 mL; average temperature 28 ° C.). The dissolution acceleration test was carried out. The results are shown in the attached FIG.

[0031]

As shown in the attached FIG. 1, in the sample of Comparative Example 1 containing only cuprous oxide, the concentration became substantially constant 10 hours after the start of the immersion, which was due to the cuprous oxide in the vicinity of the surface of the sample. Suggests the fact that the elution stops after the elutes. In the sample containing 3% of polyethylene oxide of Example 1, the elution rate gradually decreased after 2 hours from the immersion, but an asymptotic increase in the concentration was observed even after 25 hours from the immersion, and the concentration was very long. This suggests the possibility of continuously releasing copper ions.

On the contrary, 6% of polyethylene oxide
In the samples of Example 2 and Example 3 containing, the elution amount increased exponentially with the passage of time, and the elution rate of Example 3 containing 1% red iron oxide was particularly rapid. Therefore, it is presumed that the samples constituting these samples will be suitable for antifouling products in warm waters where aquatic life is intense.

Example 4 High density polyethylene (monofilament grade: MI =
1) In each, polyethylene oxide (average molecular weight of about 30
6%, 20% of cuprous oxide powder and 1% of red iron oxide powder were used to draw out from the orifice, and a monofilament having a diameter of 0.2 ^m / _m was manufactured in a usual manner.

The above monofilament was twisted into a rope shape, suspended from a position of 2 to 3 m below the sea level for 7 months from the beginning of March, and then pulled up to observe the state of aquatic organism attachment. The rope made only from HDPE used as a control had numerous aquatic organisms such as magpie, diatom and barnacle, but the rope of this example containing polyethylene oxide, cuprous oxide and red iron oxide has no organism. Was not recognized.

Example 5 Using the composition of Example 4, an injection molding machine was used to fabricate a triangle type dust container 1 for a sink shown in FIG. The above dust container was used for 6 months without cleaning, but no slimy stuff was attached to the vessel wall, and no foul odor was felt.

Example 6 EPDM with blowing agent and no blowing agent, instead 20% cuprous oxide, 5% polyethylene oxide and red iron oxide.
EPDM containing 0.5% (however, each containing a small amount of vulcanizing agent and vulcanization accelerator) was extruded from separate extruders, pressed onto a single sheet with a roll, and simultaneously vulcanized in a vulcanizer. By foaming, a sheet (thickness: about 5 mm) 11 having a dense surface layer 13 on the upper surface of the porous base layer 12 shown in FIG. 3 was obtained.

The antifouling sheet of this example is a lining for a hull that replaces the bottom paint of a ship, a lining of a waterway and a power conduit pipe,
It has various uses such as ultrasonic absorbers for submarines.

[0039]

As described above, since the antifouling composition according to the present invention is based on the thermoplastic synthetic resin, it can be formed into any shape such as filament, sheet, pipe, template, etc. Is. And cuprous oxide as an antifouling component contained in the molded product is gradually ionized through the micropores opening on the surface of the molded product as the polyethylene oxide in the composition elutes, and larvae of aquatic organisms, microorganisms, etc. Since this molded product has the effect of antifouling any article that is easily damaged by aquatic organisms for a long period of time, its use is extremely widespread.

[Brief description of drawings]

FIG. 1 is a graph showing the elution rate of copper ions from a composition of the present invention and a control composition.

FIG. 2 is a perspective view showing an example in which the composition of the present invention is applied to a dust container for a sink.

FIG. 3 is a sectional view showing an example in which the composition of the present invention is applied to a multilayer sheet.

[Explanation of symbols]

 1: Garbage container for sink 11: Multi-layer antifouling sheet 12:11 porous base layer 13:11 antifouling surface layer

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 30, 1993

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

[Object of the Invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a safe antifouling material composition resistant to contamination by aquatic organisms, algae, molds, bacteria and the like, and an antifouling product using the composition.

[0002]

2. Description of the Related Art (1) Background of the Invention In recent years, the cultivation and fishing industry has become popular, and a large amount of nets, ropes, floats and the like are used for aquaculture cages and the like. In this aquaculture facility, fishing nets, ropes, floats, etc. are soaked in seawater for a long period of time, while aquatic organisms such as maggots, diatoms, mussels, barnacles, etc. It adheres and blocks the mesh and reduces the buoyancy of the float. In particular, the blockage of the mesh hinders the inflow of fresh seawater and causes an oxygen deficiency, which reduces the growth of cultured fish and the resistance to pests and diseases, and at the same time causes a great deal of damage to the operators due to the increase of fish lost due to the sinking of the net. give. In aquaculture of yellowtail, yellowtail, etc., there is a habit of rubbing the fish body against the net to scrape off the parasites, but at that time the outer bark is damaged by the barnacles attached, and death of the pathogenic bacteria from the part causes death. The danger is also great. Similarly, in the fixed net, the attachment of aquatic organisms makes it difficult to pull up and net the net due to the increase in water flow resistance and the increase in weight.

Therefore, conventionally, fishing nets and ropes have been immersed in an antifouling treatment agent containing a copper compound, an organic tin compound or the like to prevent adhesion of aquatic organisms. However, since the antifouling effect of such an antifouling agent lasts only for about 1-2 months at the most, the trader is obliged to disinfect and antifoul the year-end net. Moreover, the use of organotin compounds has already been banned because of concern over chronic poisoning via the food chain.

Therefore, a net cage made of galvanized copper wire has been proposed as a constituent material of the cage. This metal net cage has a good shape-retaining property against waves, but it is not yet satisfactory in terms of antifouling property, corrosion resistance against seawater, and abrasion resistance. Moreover, since the zinc in the plating layer is eluted into seawater, the residual zinc in the cultured fish is more than double that of the natural fish, but this is not preferable considering the effect on the human body.

[0005] Separately, in the flatfish cultivation that has recently been increasing, almost all panel water tanks on land are used. However, the vinyl sheet used as an interior material here has no antifouling property, so that it takes about 20 days. Then, Kagaku Hazel, diatom, barnacles, etc. adhere to the entire surface of the water tank. However, since flounder has a tendency to settle in the bottom, there is a risk that lethal pathogens will invade the wound due to Kazane harbor, barnacles, etc. attached to the bottom of the aquarium. Therefore, as a countermeasure, it is necessary to remove adherent organisms about every 10 days, but not only the effort but also the stress caused by the movement of the fish, the development delay due to poor feeding, and the cause of disease induction. Is a more serious issue. The situation is the same for a concrete water tank that replaces the panel water tank.

In view of the above problems, recently, a metal having a lower potential than copper (for example, Fe, Al, Zn
Etc.), a fishing net formed by knitting a metal filament that is twisted with a synthetic fiber filament (Japanese Patent Laid-Open No. 52-1367).
No. 83), thermoplastic resins having different physical properties (for example,
An antifouling material obtained by mixing a thermoplastic synthetic resin having a low water absorption with a thermoplastic resin having a high water absorption, and mixing it with a metal powder having a high antifouling property and a high bactericidal property (Japanese Patent Laid-Open No. 63-230771).
A fishing net rope (Japanese Patent Laid-Open No. 62-33270) for braiding a fine wire made of copper alloy of a specific component and a synthetic fiber has been proposed.

Although the problems of pollution by aquatic organisms have been described above mainly in fisheries, damage by aquatic epiphytes is caused by underwater structures such as piers, piers, steel sheet piles, fenders, breakwaters, and harbors. It also occurs in floating materials such as buoys and hulls below the draft of a ship. In particular, the adhesion of marine organisms to the side of a ship causes a significant decrease in propulsion efficiency, which is a serious problem in shipping. As a simpler example, there is a garbage container in one corner of the sink, a drainage basket,
Occurrence of water stains and offensive odors caused by bacteria, mold, algae, etc. in the tableware dryer, drainage pipe, etc. is also an unpleasant phenomenon that is experienced daily.

(2) Problems of the prior art However, even with the known means described above, the sustainability of the antifouling effect,
It is not enough to satisfy the problems of productivity, production cost, etc. without contradiction. For example, Japanese Patent Laid-Open No. 63-230771 uses an antifouling material obtained by mixing a small amount of polyamide 6 resin having high water absorption in a thermoplastic polyethylene resin having low water absorption, and further mixing fine copper powder therein. A method for producing a monofilament and knitting a net by a conventional method is described. However, since the polyamide 6 itself has low water absorption and the dispersibility of the polyethylene resin is poor, the elution rate of the fine copper powder inside the monofilament is extremely slow, and therefore the antifouling ability is not sufficiently exhibited. In addition, since the miscibility between the polyethylene resin and the polyamide is poor, the latter is unevenly unevenly distributed, which reduces the strength of the fishing net. Furthermore, the methods of and are not suitable for application as an antifouling material other than the net because the method is limited to the net.

In view of the above circumstances, the applicant of the present application previously proposed the invention according to Japanese Patent Application Laid-Open No. 3-56560, and submitted a new antifouling material excellent in sustainability of antifouling effect and productivity. This antifouling material contains polyethylene oxide, a thermoplastic resin, and an antifouling metal powder (practically copper powder) as main components, and it is effective for effectively preventing the adhesion of aquatic organisms for two years or more. But expensive copper powder (market price ■■■■■■■
■ Because the use of ■■ is indispensable, there are restrictions on cost performance. In addition, since the specific gravity of copper is close to 9,
Even if it is mixed in about 20%, the weight of the entire molded product is 2.5 times or more, which is also disadvantageous to the user in terms of handling and maintenance.

[0010]

Therefore, the problem to be solved by the present invention is to solve the drawbacks of the prior art, especially the prior art of the applicant himself, and to further increase the superiority of the art. It is to provide an antifouling material.

[0011]

[Means for Solving the Problems] (1) Concept The inventors of the present invention attempted to improve the price, specific gravity, etc. of the copper powder, which had been a problem in the prior art of the applicant, and as a result of the research, Even if cuprous oxide is used instead of powder, excellent results are obtained, which is not inferior to that of copper powder, and the use of cuprous oxide can reduce the weight of molded articles by 20% or more, and is a metal with a higher ionization tendency than copper. Further, they have found that the coexistence of an oxide thereof can further increase the elution rate of copper ions, and have reached the present invention.

(2) Overview Based on the above findings, the present invention is an antifouling composition comprising a thermoplastic resin containing polyethylene oxide and cuprous oxide, and an antifouling composition using the composition. The main point is dirty molded products. In particular, the present invention, as a preferred embodiment, in addition to the above three components, an antifouling material composition containing a metal having a higher ionization tendency than copper or an oxide thereof, and an antifouling molded article using the composition. To tie. Hereinafter, various elements constituting the invention will be described by dividing them into items.

(3) Thermoplastic Resin Examples of the thermoplastic resin usable in the present invention include polyethylene, polypropylene, polyamide, polyvinylidene chloride, polyvinyl chloride, polyester, ethylene / propylene rubber, ethylene / vinyl acetate copolymer, Known thermoplastic resins such as thermoplastic polyurethane elastomers or thermoplastic elastomers are included, but considering the fishing nets that are most in demand, considering the price and miscibility with polyethylene oxide, polyolefin resins are advantageous. is there. Two or more kinds of the above thermoplastic resins may be mixed if desired.

(4) Polyethylene oxide The polyethylene oxide used in the present invention is a white powdery water-soluble thermoplastic resin which is usually obtained by ring-opening polymerization of ethylene oxide. This has an average molecular weight of 1,
Those having an average molecular weight of 5,000 to 1,000,000, especially 10,000 to 1 million can be used, although those having a dispersibility in the base thermoplastic resin, an influence on the strength at the time of mixing, and water solubility are considered. Those in the range of 500,000 are preferable.

When the average molecular weight is less than 5,000,
When processed into fishing nets, polyethylene oxide will dissolve out within a short period of time, so a long-term effect cannot be expected, and when it exceeds 1 million, the dispersibility in thermoplastic resin decreases and the strength of the net yarn itself decreases. May cause

The term "polyethylene oxide" as used in the present invention means 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 or other alkylene oxide. Is. These other alkylene oxides may be used alone or in combination of two or more.

The content of ethylene oxide in the thermoplastic resin is preferably in the range of 0.5% to 20%, preferably 2% to 10%. If it is less than 0.5%, the strength of the obtained film or monofilament is substantially the same as that of the control without addition, but preferable water solubility is not obtained.

(5) Cuprous oxide In the present invention, cuprous oxide (Cu ₂ O) is particularly selected as the antifouling metal oxide powder. It is gradually ionized like copper, has a specific gravity of about 2/3 that of copper, costs about 1/4 that of copper powder, and is commonly called orange red or tomato red. It has a bright color tone, which is based on the reason that it is similar to copper red, which is a color unique to copper. This product is a crystalline powder belonging to the equiaxed crystal system and gradually becomes black copper oxide (Cu) in moist air.
Since it changes to O), it is preferably stored in dry air or in an inert gas atmosphere before use. The content of cuprous oxide in the thermoplastic resin is 10 to 30%, preferably 15 to 30%.

(6) Easy-Ionizing Additives The composition of the present invention has a relatively small amount of copper having a higher ionization tendency than copper, that is, higher than copper on the ionization line, in addition to cuprous oxide which is an antifouling main agent. It is preferable to contain a certain metal or its oxide (easily ionizable additive). Therefore, the ionization sequence: Li>K>Rb>Cs>Ra>Ba>Sr>Ca> Na
>La>Ce>Mg>Sc>Pu>Th>Be>U> H
f>Al>Ti>Zr>Mn>V>Nb>B>Si> T
a>Zn>Cr>Ga>Fe>Cd>In>Tl> Co
>Ni>Mo>Sn>Ge>W>(H)> Cu > Hg
... Although all metals, submetals or their oxides above copper are suitable for the purpose, alkali metals and their oxides, some alkaline earth metals and radioactive elements, rare earth elements And the use of these oxides is not practical in terms of stability, safety, price, and the like. More zinc,
It is not preferable to use metals and oxides such as tin, cadmium, lead and chromium whose toxicity is considered to be a problem from the viewpoint of safety.

Considering the above circumstances, calcium oxide, magnesium, magnesium oxide, aluminum, aluminum oxide, iron, iron oxide (II and III) are considered to be suitable for the purpose, and are particularly called red iron oxide. Iron sesquioxide (Fe ₂ O ₃ ) is most preferred because it is cheap and its color tone is similar to cuprous oxide.

(7) Other additional components In the antifouling material of the present invention, if desired, various agents known as additives for thermoplastic resins, such as a foaming agent, an ultraviolet absorber, an antistatic agent and an antiaging agent. , Weathering agents, lubricants, inorganic fillers, bactericides, antifungal agents, coloring agents and the like can be added. When a rubber material such as EP rubber or EPDM is used as the synthetic resin, rubber components such as a vulcanizing agent, a vulcanization accelerator, a process oil, and zinc white are appropriately added.

(8) Shape The antifouling material of the present invention is used for molding materials such as masterbatches and pellets, as well as yarns such as monofilaments, cords, strands, bundles and chops, yarn secondary processing such as nets and ropes. Products, sheets, films, plate products such as plates,
It can be in the form of a mold material, pipe, foam material, injection molded product, hollow molded product, or the like.

The decrease in strength of the thermoplastic resin due to the addition of cuprous oxide, polyethylene oxide and an easily ionizable additive is relatively small. For example, the proportion of HDPE (high density polyethylene) is 25% by weight and 5% by weight, respectively. The decrease in tensile strength when adding cuprous oxide and polyethylene oxide is about 5% at best.

(9) Manufacturing Method The manufacturing method of the antifouling product of the present invention will be described, for example, using a polyethylene resin as a base resin as an example. That is, polyethylene oxide is mixed with polyethylene resin at a predetermined ratio, and cuprous oxide and a small amount of easily ionizable additive (eg red iron oxide) are mixed at a predetermined ratio with the mixture, and the mixture is mixed with an extruder to about 180
The mixture is heated to ˜250 ° C., kneaded, extruded into an arbitrary shape, cooled, cut, and molded into pellets to obtain a stain-proofing material for molding. As can be estimated from Example 1 and the attached FIG. 1, the elution rate of copper ions varies depending on the content of polyethylene oxide. Therefore, by adjusting the amount of polyethylene oxide added, the antifouling performance can be maintained. You can adjust it freely.

The pellets are heated to 220 to 260 ° C.,
The mixture is kneaded and extruded into a shape such as a monofilament, a multifilament, a film, a sheet, a pipe or the like through an orifice or a die according to each application, or injection molding or blow molding. If you want to obtain a foam for a float,
Pellets containing a foaming agent are placed in a female mold and molded into a predetermined shape by a one-stage or two-stage foaming method. Secondary processing of cords, ropes, etc. is performed according to a known method after the filament is processed into a yarn.

(10) Uses The use of the antifouling product according to the present invention is as a cage or stationary net,
Components or lining materials for aquariums for aquaculture such as ropes, floats, flounders, wall materials for bathrooms, garbage bins or drainers for kitchen, drainage pipes, buoys, lining materials for tethers such as buoys, hull It is any object that is easily contaminated by aquatic organisms, algae, molds, bacteria, etc., as well as lining materials under the water surface, lining materials for water power transmission pipes, etc. In particular, an antifouling sheet consisting of a rubbery foam layer and a rubbery non-foaming layer containing an antifouling agent such as cuprous oxide is a lining agent that replaces antifouling paints for ships, and is not limited to simply preventing pollution. , It is useful not only for general ships and boats but also for military ships such as submarines, because it reduces wave-making resistance and exhibits ultrasonic absorption. Furthermore, it is also useful as a lining material for water pipes and irrigation canals for hydroelectric power stations suffering from the damage of flying squirrels.

[0027]

The antifouling material according to the present invention contains water-soluble polyethylene oxide as a uniform dispersion in the base resin, and cracks and fine pores are formed in the traces of the water-soluble polyethylene oxide which are gradually eluted in water. As a result of moisture invading through the cracks and micropores of the copper, the cuprous oxide powder in the core is effectively ionized and exerts its effect for a long time. However, since the micropores and cracks generated by the elution of polyethylene oxide have a microscopic size, the strength reduction due to the micropores and cracks is relatively small as described above. Moreover, because the miscibility of the base resin and polyethylene oxide is good, a molded product with uniform strength can be obtained. Especially when the object is a yarn, there is no concern that yarn breakage will occur during drawing. Bring great benefits.

In the above, a metal or its oxide having a higher ionization tendency than copper in the composition (easily ionizable additive)
The coexistence of the above causes the easily ionizable additive to dissolve due to the cell action, promotes the formation of fine pores and fine cracks, and eventually increases the elution rate of copper ions. It should be noted that cuprous oxide, which is the main antifouling agent in the composition of the present invention, has a specific gravity of about 2 that of copper.
Since it is / 3 and the price is close to about 1/4 that of copper, it is advantageous in both use and production.

[0029]

The embodiments of the invention will be described with reference to the examples and comparative examples, but the exemplification is merely for the purpose of explanation, and does not imply any limitation or limitation of the inventive idea.

Examples 1 to 3 and Comparative Example 1 Four kinds of plate-like samples (surface area: 160 cm) having the compositions shown in Table 1 below.
² ) was prepared and immersed in a 9.8% sulfuric acid solution (liquid amount 400 ml; average temperature 28 ° C.) to carry out the dissolution acceleration test. The results are shown in the attached FIG.

[0031]

As shown in the attached FIG. 1, in the sample of Comparative Example 1 containing only cuprous oxide, the concentration became almost constant 10 hours after the start of the immersion, which was due to the cuprous oxide in the vicinity of the surface of the sample. Suggests the fact that the elution stops after the elutes. 3% of polyethylene oxide of Example 1
In the sample containing, the elution rate gradually decreased after 2 hours from the immersion, but there was an asymptotic increase in the concentration even after 25 hours from the immersion, and copper ions were continuously maintained over a very long period of time. Suggests possible release.

On the contrary, 6% of polyethylene oxide
In the samples of Example 2 and Example 3 containing, the elution amount increased exponentially with the passage of time, and the elution rate of Example 3 containing 1% red iron oxide was particularly rapid. Therefore, it is presumed that the samples constituting these samples will be suitable for antifouling products in warm waters where aquatic life is intense.

Example 4 High density polyethylene (monofilament grade: M1
= 1), 6% polyethylene oxide (average molecular weight about 300,000), 20% cuprous oxide powder and 1% red iron oxide powder, respectively
Using a mixed pellet, draw it from the orifice,
A monofilament having a diameter of 0.2 m / m was manufactured by a conventional method.

The above monofilament was twisted into a rope shape, suspended from a position of 2 to 3 m below sea level for 7 months from the beginning of March, and then pulled up to observe the state of aquatic organism attachment. The rope made only from HDPE used as a control had numerous aquatic organisms such as magpie, diatom and barnacle, but the rope of this example containing polyethylene oxide, cuprous oxide and red iron oxide has no organism. Was not recognized.

Example 5 Using the composition of Example 4, an injection molding machine was used to fabricate a triangle type dust container 1 for a sink shown in FIG. The above dust container was used for 6 months without cleaning, but no slimy stuff was attached to the vessel wall and no foul odor was felt.

Example 6 EPDM containing a blowing agent and EPDM containing no blowing agent but 20% cuprous oxide, 5% polyethylene oxide and 0.5% red iron oxide (provided that a small amount of vulcanizing agent and (Including a vulcanization accelerator) are respectively extruded from different extruders, adhered to one sheet by a roll, and then vulcanized in a vulcanizer and simultaneously foamed to form a porous base layer 12 shown in FIG.
A sheet having a dense surface layer 13 on the upper surface (thickness of about 5 m
m) 11 was obtained.

The antifouling sheet of this example is a lining for a hull that replaces the bottom paint of a ship, a lining of a waterway and a power conduit pipe,
It has various uses such as ultrasonic absorbers for submarines.

[0039]

As described above, since the antifouling composition according to the present invention is based on the thermoplastic synthetic resin, it can be formed into any shape such as filament, sheet, pipe, template, etc. Is. And cuprous oxide as an antifouling component contained in the molded product is gradually ionized through the micropores opening on the surface of the molded product as the polyethylene oxide in the composition elutes, and larvae of aquatic organisms, microorganisms, etc. Since this molded product has the effect of antifouling any article that is easily damaged by aquatic organisms for a long period of time, its use is extremely widespread.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a graph showing the elution rate of copper ions from a composition of the present invention and a control composition.

FIG. 2 is a perspective view showing an example in which the composition of the present invention is applied to a dust container for a sink.

FIG. 3 is a sectional view showing an example in which the composition of the present invention is applied to a multilayer sheet.

[Explanation of Codes] 1: Dust container for sink 11: Multi-layer antifouling sheet 12:11 porous base layer 13:11 antifouling surface layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naoko Nishisaka 3-7-17 Nitta-cho, Niihama-shi, Ehime Nihon Chemitec Corporation

Claims (4)

[Claims] 1. An antifouling material composition, which is a thermoplastic resin containing polyethylene oxide and cuprous oxide. 2. The composition of claim 1 wherein the composition comprises a metal or its oxide which has a higher ionization tendency than copper. 3. The composition according to claim 2, wherein the metal having a higher ionization tendency than copper is iron. 4. An antifouling product, which is a molded article comprising the composition according to any one of claims 1 to 3.