JPH08183861A - Agent for preventing adhesion of aquatic organism - Google Patents

Abstract

PURPOSE: To improve the durability without the possibility of environmental pollution by compounding a rubber component with a water-swelling agent and vulcanizing the compound. CONSTITUTION: 100 pts.wt. rubber component, such as a synthetic rubber or natural rubber, is compounded and kneaded with 5-100 pts.wt. water-swelling agent, 0.1-5 pts.wt. vulcanizing agent and, if necessary, 0.1-5 pts.wt. vulcanization accelerator and an age resister, a filler, an antioxidant, an antiozonant, etc., and the kneaded material is formed into sheet. This material in sheet form is vulcanized.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aquatic organism adhesion-preventing material for preventing aquatic organisms such as shellfish from adhering to solid structures installed in water such as the ocean. The present invention relates to an aquatic organism adhesion-preventing material having no fear and having excellent durability.

[0002]

2. Description of the Related Art Conventionally, it has been known that various aquatic organisms adhere to the surface of a solid substance of a fixed structure such as an intake pipe or a turret installed in rivers, lakes and marine to deteriorate the structure. There is. For example, floating material such as floats, fences, fishnets,
Water intake and drainage pipes of power plants, outer surfaces of oil fences,
For mooring lines, underwater towers and bridge legs, barnacles, mussels, mussels, bryozoans, sponges,
There is a problem that marine organisms such as ascidians, algae such as diatoms, and aquatic organisms such as seaweeds attach to them, causing their function to deteriorate and deteriorating structures. Various technologies are proposed to prevent the attachment of these aquatic organisms. Has been done.

As a paint having an action of preventing adhesion of aquatic organisms, an attempt has been made to prepare an antifouling paint by blending a water-swelling polymer with an organic binder such as rubber or synthetic resin.
As described in No. 775, there is a problem that the coating film thickness is thin and the effect is lacking in sustainability. It is necessary to repeat coating and drying to obtain a sufficient film thickness, and the method of use is complicated. . In addition, since it contains an organic solvent, it was not environmentally preferable for use in the ocean and rivers. Therefore, Japanese Patent Application Laid-Open No. 61-35735 proposes a polymer which is swollen by water and held on a support such as a woven fabric, a knitted fabric, a non-woven fabric, and a film having voids. Also,
Japanese Unexamined Patent Publication (Kokai) No. 4-69307 discloses an antifouling material containing dichlorophenyl isothiocyanates and a copper or tin compound in an antifouling paint. Further, in Japanese Unexamined Patent Publication (Kokai) No. 5-339113, there are alkyl isothiocyanates. There have been proposed marine organism anti-adhesion materials obtained by vulcanizing rubber compositions containing

However, the method of holding the water-swelling polymer on the surface of the support has a drawback of lacking in sustainability due to the small amount of the polymer which can be held on the support, and the isothiocyanates repelled by aquatic organisms are used as a paint. In the method of including in the rubber composition, the repellent is always released into the sea,
There is a problem that the effect decreases over time, and there is a further drawback that the repellent may pollute the ocean.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above-mentioned drawbacks, and an object of the present invention is that there is no fear of environmental pollution, and that the aquatic organism adhesion prevention property is high and the durability is high. Another object of the present invention is to provide an excellent aquatic organism adhesion-preventing material.

[0006]

The aquatic organism adhesion-preventing material of the present invention comprises 5 parts by weight of a rubber raw material and 5 parts by weight of a water swelling agent.
It is characterized by being compounded in an amount of up to 100 parts by weight and vulcanized.

Further, the present invention is preferably the aquatic organism adhesion preventing material as described in the above paragraph, wherein the water swelling agent is an acrylate-polyvinyl alcohol copolymer.

The present invention will be described in detail below. The water swelling agent used in the present invention is also called a super absorbent resin, refers to a polymer substance that swells by absorbing water and can retain water in the molecule, and does not include a water-soluble polymer. is there. Examples of the water swelling agent that can be used include polymers such as polyacrylic acid salt-based, polyethylene oxide-based, vinyl acetate copolymer-based, acrylic acid graft copolymer-based, and specifically, such as sodium polyacrylate. Copolymer of polyacrylic acid and polyvinyl alcohol, crosslinked sodium polyacrylate, vinyl acetate-methyl acrylate copolymer, vinyl acetate-maleic anhydride copolymer saponified product, isobutylene-maleic anhydride copolymer crosslinked product , Polyacrylonitrile hydrolyzate, Saponified starch-acrylonitrile-graft copolymer, Starch-acrylic acid graft copolymer, Polysaccharide-acrylic acid graft copolymer, Carboxymethyl cellulose cross-linked to the reaction product of cellulose and monochloroacetic acid Polyethylene oxide cross-linked product, polyvinyl chloride Alcohol cross-linked product,
Silica-based or silicate-based inorganic swelling agents such as white carbon and bentonite can be used. These water swelling agents can be used alone or in admixture of two or more. Of these, polyacrylic acid-polyvinyl alcohol copolymer, cross-linked sodium polyacrylate,
It is preferable from the viewpoints of anti-adhesion effect, safety and easy availability. The polyacrylic acid-based water swelling agent generally has a molecular weight of about 10,000 to several hundreds of thousands.

The amount of these water swelling agents added to the rubber raw material is
It is 5 to 100 parts by weight with respect to the rubber raw material, and if it is less than 5 parts by weight, the anti-adhesion effect becomes insufficient, and if it exceeds 100 parts by weight, the swelling rate of the anti-adhesion material increases and the water swelling material is sufficiently added. Both are not preferable because they are difficult to hold and the durability of the effect is reduced. From the viewpoint of anti-adhesion effect, the compounding amount is 5
50 parts by weight, more preferably 10 to 30 parts by weight.

The rubber raw material with which the water swelling agent is mixed is not particularly limited, and a general-purpose rubber raw material such as natural rubber or other synthetic rubber can be used. As the synthetic rubber used here,
Polyisoprene rubber such as cis-1,4-polyisoprene, low cis-1,4-polybutadiene, high cis-1,4
-Polybutadiene rubber such as polybutadiene, styrene-
Butadiene copolymer (SBR), ethylene-propylene-diene copolymer (EPDM), chloroprene, halogenated butyl rubber, ethylene-vinyl acetate copolymer, acrylic rubber, silicone rubber, nitrile rubber, fluororubber, acrylonitrile-butadiene rubber (NBR) etc. can be mentioned. These natural rubbers and synthetic rubbers may be used alone or in combination of two or more, but among them, from the viewpoint of processability, natural rubber and cis-
1,4-polyisoprene, styrene-butadiene copolymer, low cis-1,4-polybutadiene, high cis-1,4
-Preference is given to using polybutadiene.

As a method of blending the water swelling agent with the rubber raw material, there is a method of adding the water swelling agent and uniformly kneading them when kneading the unvulcanized rubber raw material and the auxiliary agent using a Banbury mixer or the like. To be

A rubber raw material containing a water swelling agent is vulcanized by adding a vulcanizing agent and heating to obtain an aquatic organism adhesion-preventing material. As the vulcanizing agent added at this time, sulfur can be mentioned. The amount of these used is 0.1 to 5 parts by weight, preferably 1 to 2 parts by weight, based on 100 parts by weight of the rubber raw material. If the amount is less than 0.1 part by weight, the tensile strength of the vulcanized rubber is poor,
If it exceeds 5 parts by weight, rubber elasticity is lost.

As the vulcanizing agent other than sulfur, metal oxides, organic peroxides, organic sulfur-containing compounds, reactive resins, etc. may be used or used in combination. It is determined by the type of rubber raw material.

The aquatic organism adhesion-preventing material of the present invention needs to be vulcanized after blending a water-swelling material with a rubber raw material. Vulcanization is performed by adding a vulcanizing agent to the rubber raw material mixture as described above, and heating after adding the vulcanizing agent is preferable from the viewpoint of durability of the obtained aquatic organism adhesion-preventing material.
The heating should not affect the blended water swelling agent.
It is preferably carried out at 20 to 170 ° C. The compound which is not vulcanized is inferior in strength, and further, the aquatic organism adhesion performance is not sufficiently obtained.

In the present invention, by molding an unvulcanized compound into a desired shape and then vulcanizing it, a shape suitable for the place where the aquatic organism adhesion preventing material is installed can be easily obtained. Further, the obtained aquatic organism adhesion-preventing material has a good aquatic organism adhesion-preventing effect and also has excellent durability.

A vulcanization accelerator may be added to the anti-adhesion material of the present invention. The vulcanization accelerator that can be used in the present invention is not particularly limited, but preferably M
(2-mercaptobenzothiazole), DM (dibenzothiazyldisulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), and other thiazole-based vulcanizations such as DPG (diphenylguanidine) and other guanidine-based vulcanizations Accelerator, EU (ethylene thiourea), DEU
(Diethylthiourea) and other thiourea-based vulcanization accelerators, TT (tetramethylthiuram disulfide), T
Examples thereof include thiuram-based vulcanization accelerators such as S (tetramethylthiuram monosulfide), and the amount thereof is 0.1 to 5 parts by weight with respect to 100 parts by weight of the rubber raw material.
It is preferably 0.2 to 3 parts by weight.

In the present invention, in addition to these, antioxidants, fillers such as carbon black, silica, calcium carbonate, titanium oxide, etc., which can be compounded in usual rubber compositions, zinc oxide, stearic acid, antioxidants, ozone. An additive such as a deterioration inhibitor may be blended within a range not hindering the object of the present invention in order to impart properties suitable for the purpose of use of the aquatic organism adhesion preventing material and the environment in which it is used.

The material for preventing adhesion of aquatic organisms according to the present invention is a roll,
The raw material mixture obtained by kneading with a kneading machine such as an internal mixer is molded to be suitable for the site where the inhibitor is used, and then vulcanized to obtain a sheet-like or desired sheet. This is a material for preventing the adhesion of aquatic organisms in the shape of.

[0019]

EXAMPLES Next, the present invention will be described in detail with reference to specific examples, but the present invention is not limited to the following examples.

Example 1 1-1. Manufacture of aquatic organism adhesion-preventing material Kneading rubber raw materials and water swelling agents (1) to (6) in the following composition, and adding vulcanizing agent (7) and vulcanization accelerators (8) to (10). hand,
The sheet was molded into a sheet having a thickness of 6 mm to obtain an aquatic organism adhesion-preventing material.

(1) CR (neoprene) 60 parts by weight (2) SBR 20 parts by weight (3) NR 20 parts by weight (4) Calcium carbonate 40 parts by weight (5) Silica 25 parts by weight (6) Water swelling agent (acrylic Sodium acid-polyvinyl alcohol copolymer: manufactured by Nippon Shokubai Kogyo KK, Aqualic CS: trade name 30 parts by weight (7) 0.2 parts by weight of sulfur (8) 2.5 parts by weight of magnesium oxide (9) Sulfurization accelerator (ditolylguanidine) 0.5 part by weight (10) Vulcanization accelerator (tetramethylthiuram disulfide) 1.0 part by weight 1-2. Evaluation of aquatic organism adhesion preventive property The sheet-like aquatic organism adhesion preventive material obtained above is 40 ×
It was cut into 40 cm and attached to a polyester canvas of 1 m x 1 m to give a sample for evaluation (Example 1).

Further, as comparative samples, (1) to
(6) was kneaded, and an unvulcanized composition was applied in the same manner as in Example 1 to prepare a sample (Comparative Example 1). Silicone oil was impregnated into a polyester canvas of 1 m x 1 m and dried. One (Comparative Example 2) and one (1 m × 1 m) polyester canvas in which a copper wire having a thickness of 1.5 mm was woven at 2 cm intervals were produced.

Each of the above samples was immersed in seawater for 14 months, and the adhesion of aquatic organisms was visually observed 3 months, 6 months, 9 months and 14 months after the immersion.

The evaluation criteria for observation are as follows. ⊚: Almost no adhesion of shellfish, seaweed, or algae.

○: Shellfish, seaweed, and algae are partially attached. X: Shellfish, seaweed, and algae are attached to one side.

The results are shown in Table 1.

[0027]

[Table 1]

As shown in Table 1, only a small amount of algae adhered to the portion of Example 1 of the present invention to which the aquatic organism adhesion preventive material was attached, no adhesion of shellfish was observed, and a small amount of algae adhered. It was a partial one. A large amount of shellfish and algae were found on one side of the canvas without the anti-adhesion material attached. On the other hand, the unvulcanized rubber paint of Comparative Example 1 is
After the immersion, a certain degree of anti-adhesion effect was observed for 3 months, but after 6 months it was found that the effect decreased and durability was poor. The silicone oil-impregnated cloth of Comparative Example 2 had no anti-adhesion effect. In the copper wire braided canvas of Comparative Example 3, only a small amount of shellfish and algae was found in the vicinity of the copper wire, and it was thought that the copper wire had an anti-adhesion effect, but after 9 months of immersion It was found that the copper wire deteriorated and many cut parts were observed, and the cut part increased after 14 months, resulting in poor durability.

[Examples 2 to 8] An aquatic organism adhesion-preventing material (Examples 2 to 8) was prepared in the same manner as in Example 1 except that the compounding amounts of the water swelling agents were changed as shown in Tables 2 and 3 below. ),
The swelling rate was measured. In addition, for each of them, the adhesion preventive property of aquatic organisms was evaluated in the same manner as in Example 1. Table 2 shows the results.

[Comparative Examples 5 and 6] An aquatic organism adhesion preventing material (Comparative Examples 5 and 6) was prepared in the same manner as in Example 1 except that the compounding amounts of the water swelling agents were changed as shown in Tables 2 and 3 below. ),
The swelling rate was measured. In addition, for each of them, the adhesion preventive property of aquatic organisms was evaluated in the same manner as in Example 1. The results are shown in Tables 2 and 3.

[0031]

[Table 2]

[0032]

[Table 3]

As shown in Tables 2 and 3, it was found that the swelling ratio of the aquatic organism adhesion-preventing material was increased as the blending amount of the water swelling agent was increased. Further, it has been clarified that all the samples of Examples 2 to 8 of the present invention have excellent aquatic organism adhesion-preventing property and the effect thereof is sustained.

Further, from the evaluation results of each of the above-mentioned examples, the addition of the water swelling agent to the rubber raw material is 25 to 75 parts by weight, and the swelling rate is 100 to 400%, all have excellent aquatic organism adhesion preventing effect. It was observed. On the other hand, even in the aquatic organism adhesion preventing material containing the same water swelling agent, the compound having a small amount (Comparative Example 5) cannot obtain the effect of preventing the adhesion of aquatic organisms, and the compounding amount exceeds the range of the present invention (Comparative Example). In 6), although the effect of preventing the attachment of aquatic organisms was observed, the strength decreased after 6 months and the experiment could not be continued.

As is clear from the results, the aquatic organism adhesion-preventing material of the present invention has an excellent aquatic organism adhesion effect, and the effect continues.

Since the aquatic organism adhesion-preventing material of the present invention is manufactured by mixing the rubber raw material with the water swelling agent and vulcanizing it, it has a thickness and shape suitable for the place where the aquatic organism adhesion-preventing material is used. Things can be easily manufactured. Further, a layer of an aquatic organism adhesion-preventing material can be easily formed on the surface of a fish net, rope or the like by immersing them in a rubber raw material mixture and then vulcanizing them. Since the sheet-shaped aquatic organism adhesion preventing material has sufficient strength and flexibility, it can be easily installed in a desired place and is highly practical.

[0037]

EFFECTS OF THE INVENTION Since the aquatic organism adhesion preventing material of the present invention has the above-mentioned constitution, it has an effect of preventing environmental pollution, and has an excellent aquatic organism adhesion preventing effect and its durability.

Claims (2)

[Claims] 1. A material for preventing adhesion of aquatic organisms, which comprises mixing 5 to 100 parts by weight of a water swelling agent with 100 parts by weight of a rubber raw material and vulcanizing the mixture. 2. The material for preventing attachment of aquatic organisms according to claim 1, wherein the water swelling agent is an acrylate-polyvinyl alcohol copolymer.