JPH11323869A - Organism-adhesion preventive material, execution method thereof, sea-water conveyance pipe, and ocean structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organism-adhesion preventive material capable of effectively inhibiting or preventing the adhesion of an organism such as shellfish, seaweeds, etc., for a prolonged term and also having excellent durability, etc., and an execution method thereof and a seawater conveyance pipe or an ocean structure with the organism-adhesion preventive material. SOLUTION: The organism-adhesion preventive material preventing the adhesion of shellfish and/or seaweeds is obtained by extrusion-molding a resin- containing material containing a crystalline thermoplastic resin. The organism- adhesion preventive material is fixed onto an exterior wall brought into contact with the seawater in the seawater conveyance pipe having the organism-adhesion preventive material and an adhesive packed layer fastening the organism- adhesion preventive material into the seawater conveyance pipe and the ocean structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to providing pipes and structures that come into contact with seawater, river water, etc., which can suppress or completely prevent the adhesion of shellfish and algae such as barnacles and mussels for a long period of time. A biofouling preventive material, a construction method of applying the biofouling preventive material to a seawater flow pipe, a seawater flow pipe such as a drain pipe, an intake pipe, a pipe, etc., which is provided with the biofouling preventive material, And a marine structure, such as a pier structure, a water tank, a hull, etc., provided with the biofouling preventing material.

[0002]

2. Description of the Related Art It has been considered that shellfish and algae adhere to pipes and structures in contact with seawater or river water, thereby deteriorating their functions. For example, barnacles and algae have settled on water intake pipes of thermal power plants and nuclear power plants, causing problems such as reducing the amount of water intake and blocking pipes. Since a great deal of labor and excessive costs are required to remove these shellfish and algae, various anti-fouling materials have been proposed in the past. For example, paints and chemicals such as tar epoxy paint and glass flake paint have been proposed. However, paint has a problem with durability,
The effect of preventing biofouling is short-term, and after all, frequent maintenance is required. In addition, it is necessary to consider the problem of environmental pollution in paints and chemicals.

Therefore, recently, there has been proposed a method of spraying plastic, for example, low-density polyethylene resin on the inner surface of a water pipe or the like to form a resin coating, thereby preventing the adhesion of organisms for a long period of time. However, the resin coating layer provided by thermal spraying has improved durability compared to the coating film, and has less problems of environmental pollution, but does not have a sufficient biological adhesion preventing effect, and furthermore, the resin coating layer is provided. The method itself is complicated,
In particular, there is a problem that it is difficult to construct the existing seawater pipe.

[0004] By the way, there has been conventionally known an example in which an extruded high-density polyethylene resin or the like is used for a relatively small water pipe having a hole diameter of about 5 to 20 cm or a water distribution pipe of an apartment or the like. There is no known example in which a crystalline thermoplastic resin such as an extruded polyethylene resin is applied to a seawater flow pipe including the above pipes.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a bio-adhesion which is capable of effectively suppressing or preventing the adhesion of organisms such as shellfish and algae for a long period of time, and which is excellent in durability and the like. It is an object of the present invention to provide a material for preventing seawater and a method for easily applying the material for preventing biofouling to a seawater flow pipe. Another object of the present invention is to provide a seawater pipe or a marine structure that can effectively prevent or prevent the attachment of organisms such as shellfish and algae for a long period of time, and that is excellent in durability and the like. It is in.

[0006]

Means for Solving the Problems In particular, the present inventors have developed various kinds of organisms such as barnacles, mussels and other shellfish, algae and other organisms, and slime and the like attached to various seawater pipes in contact with seawater and marine structures. Can effectively suppress or prevent adhesion for a long time,
As a result of examining various materials that can be made maintenance-free, a resin material extruded from a crystalline thermoplastic resin, especially a resin material extruded from a crystalline thermoplastic resin containing high-density polyethylene resin, Compared with the proposed low-density polyethylene resin layer obtained by thermal spraying, it has been found that the bioadhesive effect is particularly excellent, and the present invention has been completed.

That is, according to the present invention, there is provided a biofouling-preventing material for preventing the fouling of shellfish and / or algae.
Provided is a biofouling preventing material obtained by extruding a resin-containing material containing a crystalline thermoplastic resin such as a high-density polyethylene resin of 94 to 0.97 g / cm ³ . Further, according to the present invention, there is provided a method of applying the biofouling preventive material to a seawater flow pipe, wherein a resin-containing material containing a crystalline thermoplastic resin is extruded into a circular shape to obtain a cyclic biofouling preventive material, The obtained annular biofouling preventive material is introduced into the seawater flow pipe, and in the gap between the inner surface of the seawater flow pipe and the outer surface of the annular biofouling preventive material,
A method for applying a biofouling preventive material, characterized by filling an adhesive filler and fixing an annular biofouling preventive material, is provided. Further, according to the present invention, it is characterized by comprising a seawater flow pipe, the biofouling prevention material provided in the seawater flow pipe, and an adhesive filling layer for fixing the biofouling prevention material in the seawater flow pipe. A seawater conduit is provided. Further, according to the present invention, there is provided a marine structure, wherein the biofouling-preventing material is fixed to an outer wall of the marine structure in contact with seawater.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail. The biofouling-preventing material of the present invention, even when exposed to river water or seawater for a long time, effectively suppresses or prevents the adhesion of shellfish and algae such as barnacles and mussels, and has excellent durability. It is a ring-shaped or plate-shaped material obtained by extruding a resin-containing material containing a crystalline thermoplastic resin.

The crystalline thermoplastic resin is an extrudable resin, for example, a polyolefin, specifically, a polyethylene resin. The polyethylene resin may be a homopolymer of ethylene or a copolymer of ethylene and another olefin. Examples of the olefin include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene,
And α-olefins having 2 to 10 carbon atoms such as -decene. In order to further improve the effect of preventing biofouling, it is particularly preferable to contain a high-density polyethylene resin having a density of 0.94 to 0.97 g / cm ³ . The density of the high-density polyethylene resin is, in particular, 0.945 to 0.960 g.
/ Cm ³ is preferable, and the melt index (value measured in accordance with JIS K6760) is 0.0
One to 2 g / 10 minutes is preferred. As such a high-density polyethylene resin, commercially available products can also be used. For example, trade names “Nisseki Plast-KE071A”,
"Nisseki Plast-KE061A", "Nisseki Plast-K"
E051Z "and" Nisseki Plast-KE141A "(all manufactured by Nippon Petrochemical Co., Ltd.).

The blending ratio of the crystalline thermoplastic resin in the resin-containing material used in the biofouling preventive material of the present invention is not particularly limited as long as it can be extruded, but is preferably 50% by weight or more and 90 to 100% by weight. % Is desirable. When the high-density polyethylene resin is contained in the crystalline thermoplastic resin, the mixing ratio of the high-density polyethylene is 30% by weight or more, particularly 80 to 1%, based on the total amount of the crystalline thermoplastic resin.
A range of 00% by weight is preferred.

Various additives can be added to the resin-containing material in order to further improve the physical and chemical performances and further the bioadhesive action. Specifically, additives selected from the group consisting of antioxidants, antistatic agents, light stabilizers, lubricants, antiblocking agents, coloring agents, fillers, flame retardants, biological repellents, and mixtures thereof, and the like. No.

Examples of the antioxidant include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and mixtures thereof, which are usually used for polyolefins. Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol (BHT), o-tert-butyl-p-cresol (BHA), tetrakis (methylene-3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate) methane, 4,4'-butylidenebis (6
-Tert-butyl-m-cresol) (SWP),
1,1-bis (4-oxyphenyl) cyclohexane,
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzene),
2,6-bis (2'-hydroxy-3'-tert-butyl-5'-methylbenzyl) -4-methylphenol, 2,2-thiobis (4-methyl-6tert-butylphenol), 4,4-thiobis (3-methyl-6-
tert-butylphenol), hydroxychroman derivatives such as p-hydroxy-diphenylamine, and tocopherol. Tris (2,4-di-tert-butylphenyl) is used as the phosphorus antioxidant.
Phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-diphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4-biphenylenediphosphite and the like Is mentioned. Examples of the sulfur-based antioxidants include dilauryl-thiodipropionate (DLTP), distearylthiodipropionate (DSTP), mercaptobenzimidazole, 2,2-tert-butyl-4-.
Methylphenol sulfide and the like can be mentioned. Examples of the amine-based antioxidant include phenyl-β-naphthylamine and N, N′-phenylcyclohexyl-p-phenylenediamine. The compounding ratio of the antioxidant is
With respect to 100 parts by weight of the crystalline thermoplastic resin, 0.0
The amount is preferably 1 to 0.5 part by weight, particularly preferably 0.01 to 0.3 part by weight. When two or more antioxidants are used in combination, it is desirable to mix them so that the total amount is within the above range.

As an antistatic agent, fatty acids having 1 carbon atom
And 6-22 fatty acid monoglycerides, fatty acids, alkylamine derivatives, and mixtures thereof. Examples of the fatty acid monoglyceride having 16 to 22 carbon atoms of the fatty acid include monoglyceride stearate, monoglyceride palmitate, and the like. As the fatty acids, linear saturated fatty acids, branched saturated fatty acids, unsaturated fatty acids,
Resin acids and the like, specifically, lauric acid, myristic acid, palmitic acid, linoleic acid, linolenic acid, stearic acid, isostearic acid, arachinic acid, behenic acid,
Examples thereof include 12-hydroxystearic acid and abietic acid, and particularly preferred is palmitic acid and stearic acid.
These can be used alone or as a mixture when used. Examples of the alkylamine derivative include octyldiethanolamine, decylethanolamine,
Dodecyldiethanolamine, hydroxydodecyldiethanolamine and the like can be mentioned, and when used, they can be used alone or as a mixture. These antistatic agents can be appropriately blended in a desired blending ratio.

As the light stabilizer, benzophenone derivatives, salicylic acid esters, benzotriazole derivatives,
Organic tin compounds, carbon black and the like can be mentioned. The compounding ratio of the light stabilizer is usually 2 to 3 of the total amount of the resin-containing material.
It can be blended in the range of weight%.

Examples of the lubricant include fatty acid metal salts and fatty acid metal soaps. Examples of the fatty acid metal salt include a metal salt of a carboxylic acid having 7 to 26 carbon atoms, preferably 11 to 21 carbon atoms. Specific examples include sodium, magnesium, calcium, and zinc salts of linear aliphatic carboxylic acids such as lauric acid, palmitic acid, stearic acid, and behenic acid. The mixing ratio of the lubricant is preferably 0.01 to 0.4 parts by weight based on 100 parts by weight of the crystalline thermoplastic resin. If the amount exceeds 0.4 parts by weight, molding defects such as foaming during extrusion molding may occur, which is not preferable. When two or more kinds are used in combination, it is desirable to mix them so that the total amount is within the above range.

Examples of the filler include various metal compounds, carbon fiber, glass fiber and the like. Examples of the metal compound include metal oxides such as magnesium oxide, calcium oxide, aluminum oxide, silicon dioxide, and titanium dioxide; and metal hydroxides such as magnesium hydroxide, calcium hydroxide, calcium hydroxide, aluminum hydroxide, and orthotitanic acid. Metal carbonates such as potassium carbonate, sodium hydrogen carbonate, sodium carbonate, magnesium carbonate, calcium carbonate; metal sulfates such as magnesium sulfate, calcium sulfate, barium sulfate, aluminum sulfate; sodium metasilicate, anhydrous sodium silicate, metasilicate Lithium oxide,
Examples include silicates such as anhydrous lithium silicate, potassium metasilicate, anhydrous potassium silicate, magnesium silicate, magnesium metasilicate, calcium silicate, and aluminum silicate. These may be a natural product or a synthetic product, and examples of the natural product include talc, bentonite, and hydrotalcite. These can be used alone or as a mixture when used. The mixing ratio of the filler is preferably 0.01 to 0.4 parts by weight based on 100 parts by weight of the crystalline thermoplastic resin. If the amount exceeds 0.4 parts by weight, molding defects such as foaming during extrusion molding may occur, which is not preferable. When two or more kinds are used in combination, it is desirable to mix them so that the total amount is within the above range.

[0017] Examples of the biological repellent include sodium chloride and the like, which can be appropriately added in an appropriate amount.

In addition to the resin-containing material used in the present invention, a powdery paraffin, a powdery ester compound, a higher alcohol, a fat or oil component such as amide, a silicon derivative or the like can be added.

To extrude the resin-containing material,
For example, using a laminating type, a pump type, a screw type or the like, an extruding machine can be used to extrude into a ring shape, a plate shape or the like. The extrusion temperature during extrusion molding is usually from 120 to 2
The temperature is 50 ° C, preferably 125 to 200 ° C, particularly preferably 130 to 190 ° C, and the extrusion speed can be appropriately selected depending on the shape to be extruded, the size, and the like.
Usually, it can be performed in a range of 1 cm to 100 m / min. The take-off device is not particularly limited, and may be a caterpillar type or a roll type. The cooling device may be either water-cooled or air-cooled, and may be direct cooling or indirect cooling.

The biofouling preventive material thus extruded can be used after being cut into a desired size. Further, the thickness of the biofouling preventing material can be appropriately selected according to the place of use, but is usually 0.1 to 50.
mm, preferably about 1 to 40 mm. When the biofouling prevention material is made into a ring, the diameter is 10 cm to 5 m.
The degree is appropriate.

In the method for applying a biofouling preventing material of the present invention,
The annular material of the biofouling prevention material is introduced into a seawater flow pipe such as a drain pipe through which seawater flows, an intake pipe, a pipe, and the like, and a gap between the inner surface of the seawater flow pipe and the outer face of the annular biofouling prevention material, Fill the adhesive filler to fix the biofouling inhibitor.

Seawater flow pipes such as drain pipes, water intake pipes, and pipes
Usually, it is made of metal such as iron, but the material is not particularly limited. The inner diameter of the seawater pipe is usually 25cm-5m
It is preferable that the outer diameter of the annular biofouling preventing material introduced into the seawater flow pipe is 10 to 20 mm smaller than the inner diameter of the introduced seawater flow pipe. That is, the thickness of the adhesive filler layer formed by the adhesive filler described below,
It is preferably from 10 to 20 mm. The adhesive filler is not particularly limited as long as it can adhere and fix a biofouling preventive material such as various cement materials and adhesives in the seawater flow pipe.

The seawater passage pipe of the present invention can be obtained by the above-mentioned construction method or the like, and comprises a seawater passage pipe, the above-mentioned organism-adhering material, and an adhesive filling layer for fixing the organism-adhering material in the seawater-water pipe. And The inner diameter of the seawater conduit is 25
cm to 5 m, and the thickness of the adhesive filling layer is 10 to 2
0 mm is preferred. Further, the biofouling preventing material may have a multilayer structure.

The marine structure of the present invention has the above-mentioned anti-biofouling material fixed to an outer wall in contact with seawater. The marine structure includes a pier structure, a water tank, a hull, and the like. The shape of the biofouling preventing material can be appropriately selected according to the outer shape of the marine structure to be fixed. The fixing method is not particularly limited, and examples thereof include fixing with an adhesive and fixing with a bolt.

[0025]

The biofouling-preventing material of the present invention is obtained by extruding a specific resin-containing material, so that the fouling of living organisms such as shellfish and algae can be effectively suppressed or prevented for a long time. In addition, it is excellent in durability and the like, and can also suppress or prevent slime adhesion. Therefore, it is useful as a biofouling preventing material in a marine structure such as a seawater flow pipe such as a drain pipe, an intake pipe, and a pipe through which seawater flows, a pier structure, a water tank, and a hull. Moreover, in the construction method of the present invention, since the extruded biofouling preventing material is used, the biofouling preventing material can be easily constructed on the seawater flow pipe. Further, since the seawater flow pipe and the marine structure of the present invention are provided with the biofouling preventive material, the fouling of marine organisms such as shellfish and algae can be effectively and for a long time suppressed or prevented, and the durability is improved. It is excellent in performance and can be expected to be maintenance-free.

[0026]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 A commercially available pellet-shaped high-density polyethylene (trade name "Nisseki Plast-KE051Z", manufactured by Nippon Petrochemical Co., Ltd., melt index 0.15 g / 10 min, density 0.950 g / cm) ³ , hardness (Shore hardness D) 65)
A melt containing 3% by weight of carbon black was melt-extruded at an extrusion speed of 50 cm / min and a temperature of 180 ° C.
After passing through a sizing device, it is cooled in a water tank and the outer diameter is 7
A high-density polyethylene tube having a thickness of 50 mm and a thickness of 25 mm was manufactured. The obtained high-density polyethylene pipe is installed inside a ready-made iron drainage pipe, cement is poured between the ready-made pipe and the high-density polyethylene pipe, and a high-density polyethylene layer is fixedly formed inside the ready-made pipe. Was prepared. The obtained drainage pipe was immersed in seawater for one year, but no occurrence of shellfish such as barnacles was observed.

COMPARATIVE EXAMPLE 1 A steel intake pipe was ground-treated by grit blasting, and then commercially available powdered low-density polyethylene was thermally sprayed on the inner surface of the intake pipe to form a low-density polyethylene layer. When the obtained intake pipe was immersed in seawater for one year, adhesion of shellfish such as barnacles was observed.

Example 2 The same high-density polyethylene and carbon black melt as in Example 1 was melt-extruded at an extrusion rate of 50 cm / min at a temperature of 170 ° C., passed through a sizing device, and cooled in a water bath. A high-density polyethylene sheet having a thickness of 3 mm and a width of 1 mm was manufactured. The resulting high-density polyethylene sheet was immersed in seawater for one year, but no occurrence of shellfish such as barnacles was observed.

Claims (6)

[Claims] 1. A biofouling preventive material for preventing the adhesion of shellfish and / or algae, which is obtained by extruding a resin-containing material containing a crystalline thermoplastic resin. 2. A crystalline thermoplastic resin having a density of 0.9
Anti-biofouling material according to claim 1, characterized in that it comprises a high density polyethylene resin 4~0.97g / cm ^3. 3. The resin-containing material is selected from the group consisting of an antioxidant, an antistatic agent, a light stabilizer, a lubricant, an anti-blocking agent, a coloring agent, a filler, a flame retardant, a biological repellent, and a mixture thereof. The biofouling inhibitor according to claim 1 or 2, further comprising an additive. 4. A method for applying the anti-fouling material according to any one of claims 1 to 3 to a seawater flow pipe, comprising extruding a resin-containing material containing a crystalline thermoplastic resin into a ring shape. To obtain an annular biofouling preventive material, and introduce the obtained annular biofouling preventive material into the seawater flow pipe.The adhesive filler is inserted into the gap between the inner surface of the seawater flow pipe and the outer face of the annular biofouling preventive material. A method for constructing an anti-biofouling material, characterized in that the material is filled to fix an annular anti-fouling material. 5. A seawater passage pipe, the organism-adhering material according to any one of claims 1 to 3 provided in the seawater passage tube, and the organism-adhering material is fixed in the seawater passage tube. A seawater flow pipe comprising an adhesive filling layer. 6. A marine structure, wherein the biofouling-preventing material according to any one of claims 1 to 3 is fixed to an outer wall of the marine structure in contact with seawater.