JP2006160665A - Marine organism adhesion-preventing agent and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive marine organism adhesion-preventing agent which has high safety and high repelling effect persistency. <P>SOLUTION: This sustained release marine organism adhesion-preventing agent is obtained by including a natural organism-originating repelling ingredient with a water-insoluble cyclodextrin (CD). Allyl isothiocyanate and a peracylated cyclodextrin (CD) are used as the organism-originating repelling ingredient and the water-insoluble cyclodextrin, respectively, to obtain the marine organism adhesion-preventing agent. The marine organism adhesion-preventing agent is kneaded with concrete or coated on the bottom of a ship. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a marine organism adhesion inhibitor and use thereof. More specifically, the present invention relates to an anti-adhesion agent for highly stable marine organisms using an organism-derived repellent component and use thereof.

  In thermal power plants and steelworks factories that use seawater, marine organisms such as blue mussels, barnacles, and algae attach to the water inlets of the cooling water system, increasing fuel consumption due to increased seawater resistance, Various adverse effects such as the progress of corrosion have occurred. In addition, when these marine organisms adhere to aquaculture nets, stationary nets, ship bottoms, etc., the passage of seawater is obstructed, killing cultured fish due to lack of dissolved oxygen, net subsidence, etc. Damage such as decline has occurred.

In order to remove these marine organisms, in the case of ships, it is necessary to enter dogs at regular intervals, and in the case of using nets, it is necessary to stop the temporary operation and remove attached marine organisms. Therefore, there is a problem that a great burden is imposed on the workers. Therefore, in order to prevent the adhesion of these marine organisms, paints and the like to which an adhesion preventing agent such as organotin compounds and heavy metals are added have been used.
Since these anti-adhesive agents produce substances that are toxic to marine organisms by metal ions, they exhibited excellent anti-adhesion effects due to their growth-inhibiting effects and killing. However, their use is prohibited due to their toxicity, accumulation in the environment, and the effects of environmental hormones on living organisms. At present, various compounds such as cuprous oxide, dithiocarbamic acids, and triphenylborane complex compounds are proposed instead. And used (see, for example, Patent Document 1). However, copper nitrite and the like are also subject to regulation in the long term as environmental hormones, and since they require a higher concentration of elution than organotin, there is concern about accumulation in the environment and ecosystem.

On the other hand, as a method for suppressing the attachment of marine organisms with low environmental impact, barnacles promoted by biofilms by removing the adherent bacterial clusters (biofilms) produced in the initial stage of biofouling with lytic enzymes Methods have also been developed that inhibit larvae adherence and consequently prevent attachment of large adherents. However, it is economically difficult to mass-cultivate the lytic enzyme required for the paint. In addition, a method of extracting an adhesion inhibitor that does not attract other attached organisms from a part of natural marine organisms and using it in paints has been developed. However, it has low activity and is non-selective even if it has high activity. There are problems such as producing toxicity and ensuring a sufficient amount for isolating components. Therefore, it has been desired to develop an anti-fouling agent for marine organisms that is highly safe for the environment and ecosystem, has a high repellent effect, and is inexpensive.
JP-A-8-295829

  It is an object of the present invention to provide a marine organism adhesion preventive agent that is highly safe to the environment and ecosystem, has a high repellent effect, and is inexpensive. More specifically, an object of the present invention is to provide a sustained-release marine organism anti-adhesion agent that can maintain the sustainability of the repellent effect by utilizing a component derived from a natural organism as a repellent component of a marine organism.

As a result of diligent research to solve the above problems, the present inventors have used marine organism-derived repellent components such as spices as marine organism repellent components, thereby reducing the impact on the environment. The present inventors have found that a biological anti-fouling agent can be provided and have completed the present invention.
These natural substances are easily decomposed by microorganisms, heat, light, and the like, and because they are water-soluble, it is difficult to maintain their repellent effect in seawater. Therefore, the present inventors enclose these components having a repellent effect with water-insoluble or poorly water-soluble cyclodextrin (CD), thereby maintaining the repellent effect even in seawater. Can be provided.

That is, the present invention relates to a marine organism adhesion inhibitor and the use thereof according to any one of (1) to (5) below.
(1) A marine organism anti-adhesion agent comprising clathrating a biological repellent component with a water-insoluble cyclodextrin (CD) or a sparingly water-soluble cyclodextrin (CD).
(2) The marine organism adhesion inhibitor according to (1) above, wherein the water-insoluble cyclodextrin (CD) or the sparingly water-soluble cyclodextrin (CD) is a peracylated cyclodextrin (CD).
(3) The anti-adhesion agent for marine organisms according to either (1) or (2) above, wherein the organism-derived repellent component is derived from a plant.
(4) The anti-adhesion agent for marine organisms according to (3) above, wherein the organism-derived repellent component is allyl isothiocyanate (AITC).
(5) Use of the marine organism adhesion inhibitor according to any one of (1) to (4).

  The anti-adhesion agent for marine organisms of the present invention contains a repellent component derived from natural organisms as an active ingredient, and therefore has high safety to the environment and ecosystem. In addition, since it is water-insoluble or sparingly water-soluble, the repellent effect is highly sustainable and economical. Therefore, it is possible to prevent marine organisms from adhering to the cooling water system water inlets and marine structures in thermal power plants and steelworks factories, thereby reducing the labor and costs associated with the removal and disposal of adhering marine organisms. be able to.

  The “marine organism adhesion preventing agent” of the present invention refers to a substance that prevents the adhesion of marine organisms by containing a repellent component derived from organisms. The target marine organisms include mussels, barnacles, hydroworms, bryophytes, sea squirts, and algae, which avoid the repellent components contained in the anti-adhesive agent, thereby allowing the water outlets and offshore structures of the factory cooling water system Adhering to the bottom of the ship is hindered.

“Biological repellent component” contained in the anti-adhesive agent of the present invention refers to a repellent component of marine organisms obtained by extraction, separation, etc. from plants and animals, and has high safety to the environment and ecosystem. It means a non-toxic or low-toxic component having irritation such as pungent taste.
As plant-derived repellent components, for example, tannin, hiba oil, cypress oil, cinnamic acid, gallic acid, forsythia extract, kumazasa extract, jongso bamboo extract, mustard, horseradish oil, egonoki extract, honoki extract, neem extract A thing etc. can be illustrated. Moreover, chitosan, protamine, etc. can be illustrated as an animal-derived repellent component. Furthermore, these active ingredients can be artificially synthesized. Examples of such components include tropolone-based organic compounds such as hinokithiol, which is a main component of hiba oil and cypress oil, or 2,6-dimethoxy-1,4-benzoquinone, which is a main component of Kumazasa extract and Soso bamboo extract. And allyl isocyanate compounds which are main components of mustard and wasabi oil.

  Other examples of the repellent component include spices such as cinnamon, caraway, oregano, thyme, clove, lemon, nutmeg, laurel, saffron, coriander, yam, marjoram, vanilla and the like. Furthermore, the active ingredient can also be artificially synthesized. As such components, for example, cinnamaldehyde, cinnamic alcohol, carvone, carvacrol, thymol, eugenol, limonene, β-pinene, cineol, safrole, linanol, which are components of these spices, Citronellol, terpineol, vanillin and the like can be mentioned.

  Among the repellent components of the present invention, it is particularly preferable to use allyl isothiocyanate (hereinafter referred to as AITC) that is pungent and rich in volatility as the repellent component. AITC is a component that has already been approved by the Food Sanitation Act and laws concerning the examination of chemical substances and regulations on manufacturing, etc., and is widely used in food as a component of wasabi and mustard, to the non-toxic environment and ecosystem It is a highly safe ingredient. On the other hand, it is difficult to handle due to the irritation and volatility of AITC, and because it is easily water-soluble, there is a problem that it is difficult to maintain the repellent effect in seawater for a long time. It is more preferable to improve these by inclusion with a water-soluble substance.

  The “water-insoluble cyclodextrin (CD) or poorly water-soluble cyclodextrin (CD)” of the present invention is a water-insoluble or poorly water-soluble material by acyl-substituting all hydroxyl groups of water-soluble natural CDs. This refers to peracylated CDs that can be used as inclusion materials for repellent ingredients. Peracylated CD includes peracetylated αCD, peracetylated βCD, peracetylated γCD, perpropionylated αCD, perpropionylated βCD, perpropionylated γCD, and other C4-20 carboxylic acids and αCD, βCD, γCD Examples of peresterified compounds with all of the hydroxyl groups of these groups include peracylated αCD, peracylated βCD, peracylated γCD, etc., which are used by mixing two or more of these carboxylic acids. Of these CDs, water-insoluble peracetylated αCD or peracetylated γCD is particularly preferably used as an inclusion material for repellent components, and peracetylated αCD is particularly preferable.

  On the other hand, the present inventors have confirmed that these water-insoluble or poorly water-soluble CDs are readily soluble in organic solvents such as ethyl acetate and acetone. Therefore, by utilizing this characteristic, it is possible to stabilize the inclusion of biological repellent components in these water-insoluble or sparingly water-soluble CDs using an organic solvent or a mixed solvent of an organic solvent and water. The clathrate obtained in this way is water-insoluble or sparingly water-soluble so that it has water resistance when used as an anti-adhesive agent in concrete, etc. Can be released. Thereby, the repellent effect and the antibacterial effect which the repellent component originally has can be satisfactorily maintained for a long time in seawater.

The anti-adhesive agent of the present invention depends on the amount of evasion tax and the type of cyclodextrin and organic solvent used as an inclusion substance, but after dissolving 0.1-50 g of cyclodextrin in 100 g of organic solvent, 0.01 ~ It can be prepared by adding 10 g of repellent ingredients and mixing. In particular, after dissolving 10 g of peracetyl αCD with 100 g of dioxane, 1 g of AITC is added as a repellent component and mixed together to obtain a highly effective anti-adhesive agent. These anti-adhesive agents can be prepared by any method if cyclodextrins and repellents are mixed in an organic solvent.
Any organic solvent can be used as long as it can dissolve water-insoluble or sparingly water-soluble cyclodextrins, especially peracetyl αCD, peracetyl βCD, and peracetyl. When γCD is used, tetrahydroxyfuran (hereinafter abbreviated as THF), ethyl acetate, chloroform, methyl ethyl ketone (hereinafter abbreviated as MEK), methylene chloride, dimethylformamide (hereinafter abbreviated as DMF), acetic acid, It is preferable to use dioxane or acetone as a solvent.

  The “use of the anti-adhesive agent” of the present invention means that the anti-adhesive agent of the present invention is used for products such as resin lining, concrete products, ship bottom paint, fish nets and pollutants for preventing diffusion of pollutants, and to fibers. It is used for the coating and kneading of water and using these products to prevent the attachment of marine organisms to marine structures and ships and other objects. The anti-adhesion agent of the present invention is non-toxic or has low toxicity, is easy to handle as a product, and can be procured sufficiently even for use in large quantities. Moreover, since it has a repellent effect over a long period from its sustained release, it can be used effectively.

  For example, the anti-adhesive agent of the present invention can be kneaded into an elastomer, synthetic resin, concrete or the like and used as an anti-adhesion product with sustained release. Various rubbers and thermoplastic elastomers can be used as the elastomer. Specifically, natural rubber (NR), polyisoprene rubber (IR) acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), butyl rubber (IIR), ethylene propylene rubber (EPDM), chlorosulfonated polyethylene Rubber (CSM), butadiene rubber (BR), halogenated butyl rubber (CIIR, BIIR), fluoro rubber (FKM), silicone rubber (Q), urethane rubber (U), chlorinated polyethylene rubber (CPE) and styrene elastomer ( SBS, SIS, SEBS), olefin elastomer (TPO), urethane elastomer (TPU), vinyl chloride elastomer (TPVC), polyester elastomer (TPEE), polyamide elastomer (PAE) and the like can be used.

The synthetic resin may be either a thermoplastic resin or a thermosetting resin. For example, a polyolefin resin, a polyester resin, an epoxy resin, a phenol resin, a fluorine resin, or the like may be used. More specifically, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), bisphenol type epoxy resin, and the like can be used.
Furthermore, concrete can be used as a concrete panel or PC panel by directly applying and impregnating an adhesion inhibitor to the concrete, or coating or lining a resin containing the adhesion inhibitor on the concrete surface. It can be used for bridge piers, quay walls, steel sheet piles on “coasts”, “seawater intake channels”, “drainage channels”, “sewage treatment plant discharge channels” at power plants and factories.

  These sustained-release anti-adhesion products are made by adding a biological repellent component or inclusion substance to a synthetic resin or elastomer together with a necessary compounding agent, kneading using a kneading apparatus such as a roll or a Banbury mixer, and then It can be obtained by molding into an appropriate shape and performing vulcanization treatment, curing treatment, etc. as necessary. Therefore, for example, in order to obtain concrete containing an anti-adhesive agent, it is necessary to add an anti-adhesive agent with a cement weight ratio of about 1 to 5% for both mixing and impregnation of the concrete. Can be expected.

In addition, by blending the anti-adhesive agent of the present invention using a polar solvent, it can be used as a liquid agent for forming a coating film on a bottom of a ship, a fish net, a drain outlet panel, etc. Can be used. For example, when obtaining a paint containing an anti-adhesive agent, the anti-adhesion effect of marine organisms can be prevented for at least 3 months and 2 years by adding 20% or less, preferably about 10% of the anti-adhesive agent to the paint. A ship bottom paint that can be maintained can be obtained. Specific examples of the polar solvent include alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, and tert-butanol, and ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, and dipropylene glycol. , Tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tripropylene glycol Examples thereof include glycol solvents such as monomethyl ether. In addition, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and the like, and ether solvents such as dioxane, tetrahydrofuran, ethyl ether and the like, and ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, etc. And aromatic solvents such as benzene, toluene, xylene, methylnaphthalene and solvent naphtha, and other halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform and methylene chloride, and polar such as dimethylformamide, dimethyl sulfoxide and acetonitrile. A solvent etc. can also be illustrated. These solvents can be used alone or in combination of two or more.
Hereinafter, the details of the present invention will be described with reference to examples and the like, but the present invention is not limited thereto.

Preparation of anti-adhesive agent AITC (manufactured by Aldrich) was used as a repellent component of marine organisms. After dissolving 4.0 g of peracetyl αCD (manufactured by Wakka) in 10.3 g of dioxane (manufactured by Wako Pure Chemical Industries, Ltd.), 100 mg of AITC was added and mixed by inversion until uniform to prepare 14.4 g of an anti-adhesive agent.

Use of anti-adhesive agent Peracetyl αCD (manufactured by Wakka) 20g, dioxane (manufactured by Wako Pure Chemical Industries) 51.5g, AITC 500mg, kneaded 72g of anti-adhesive agent prepared in the same manner as in Example 1 in concrete. A concrete board (300 × 300 × 20 mm, weight 4 kg) containing dust and an adhesion inhibitor was prepared. For comparison, a concrete board (300 x 300 x 20 mm, 4 kg in weight) that does not contain an anti-adhesive agent is used as a control, both hung at a height that does not come out to the water surface at low tide, immersed in the ocean, The state of prevention of organism adhesion was observed.

As a result of observation from the start of immersion 3 months after installation, adhesion of 3 mussels and 4 barnacles was confirmed from the control board, but concrete containing AITC as a repellent component was kneaded. No marine organisms were attached to the board.
[Reference Example 1]

Examination of solubility of percetylated CD Peracetyl αCD, peracetyl βCD, and peracetyl γCD were each dissolved in 100 g of various solvents, and the amount dissolved in each solvent was examined. As the solvent, THF, ethyl acetate, chloroform, MEK, methylene chloride, DMF, acetic acid, dioxane, acetone, dimethyl sulfoxide (hereinafter abbreviated as DMSO), methanol, ethanol, toluene, isopropyl alcohol, hexane, and water were used. Solvents other than water were those manufactured by Wako Pure Chemical Industries.

Results The dissolved amounts of peracetyl αCD, peracetyl βCD, and peracetyl γCD are shown in FIGS. 1, 2, and 3, respectively. The arrows in the figure indicate that 100 g or more can be dissolved in each solvent, and it was confirmed that all of these cyclodextrins are soluble in organic solvents such as THF and ethyl acetate. On the other hand, it was confirmed that peracetyl αCD and peracetyl γCD are insoluble in water, and peracetyl βCD is poorly water-soluble. Therefore, by using these as inclusion bodies, dissolution of repellent components in seawater can be prevented.
[Test Example 1]

Anti-adhesion test for marine organisms An anti- adhesion agent prepared in the same manner as in Example 1 was applied to a test board in four places so as to form a circle having a diameter of 4 cm (FIG. 4a). The anti-adhesion agent was colored light brown so that it could be visually observed, and the coated surface was also slightly colored. After the anti-adhesive agent was dried, the mussel (4 individuals) was placed between the part where the anti-adhesive agent was applied and the part where the anti-adhesive agent was not applied, and fixed with an adhesive (FIG. 4b). Since the shellfish is fixed, it cannot move around, but even in this state, the tentacles can be freely extended forward (side where the anti-adhesive agent is applied) or after (side where the anti-adhesive agent is not applied). Therefore, the board was submerged in running water, and the number of tentacles stretched after 3 hours was observed (Fig. 4c). The outline of this test and the number of tentacles of shellfish stretched are shown in FIG. Under the test conditions, if the anti-adhesive agent has no anti-adhesion effect, the shellfish will freely extend the tentacles back and forth, and if there is an anti-adhesion effect, the test results will not be extended before. Evaluated.

Results It was confirmed by visual observation that coloring by the anti-adhesive agent was maintained even after the test board was exposed to running water by coloring the application surface of the anti-adhesive agent. Thus, it was shown that the anti-adhesive was effectively maintained on the board throughout the test. Further, as shown in FIG. 4c, no tentacles were stretched in the range where the adhesion preventing agent was applied, and a high adhesion preventing effect was confirmed.
[Comparative Example 1]

Preparation of test agent Instead of AITC used as a repellent component, 100 mg of iodine was used, 2 g of peracetyl αCD (manufactured by Wakka) was used, and a test agent prepared using 10 g of dioxane (manufactured by Wako Pure Chemical Industries, Ltd.) In the same manner as in Test Example 1 and FIG. 4a, 2 to 3 places were applied to the test board. In addition, a solution of 125 g of copper sulfate pentahydrate (CuSO ₄ · 5H ₂ O) dissolved in water with a total amount of 1 kg was used as a test agent, and applied so that 1 mg of copper sulfate adhered within a 4 cm diameter circle. . The test agent was applied and dried, and mussels (4 individuals) were fixed in the same manner as in the test example and FIG. 4b, and the number of tentacles stretched was observed as in test examples 1 and 4c. The test agent containing iodine was also observed when it was applied 2-3 times. Table 1 shows the number of tentacles in each individual and the average.

Results In the test agent containing iodine, there were individual differences among mussels, but it was confirmed that the tentacles were extended more on the coated side than on the uncoated side. On the other hand, the test agent containing copper sulfate pentahydrate (CuSO ₄ · 5H ₂ O), which has a repellent effect, has individual differences in mussels, but the tentacles are almost extended to the coated side compared to the uncoated side. In addition, the presence of the repellent component was confirmed to have an adhesion preventing effect. However, the anti-adhesive agent using AITC as a repellent component does not extend the tentacles at all, so compared to copper sulfate pentahydrate (CuSO ₄ · 5H ₂ O), which has been known as an anti-adhesion substance, It was shown that the anti-adhesion agent using AITC of the present invention has a higher anti-adhesion effect.

  By using the anti-adhesive agent of the present invention, it becomes possible to prevent the attachment of marine organisms to the water outlets and marine structures of the cooling water system of power plants and factories. Can be reduced. Moreover, by using it for ship bottom paint, it can be used for maintaining the driving force of the ship by preventing adhesion of marine organisms.

It is a figure showing the amount of peracetyl alphaCD dissolved in a solvent (reference example). It is a figure showing the amount of peracetyl βCD dissolved in a solvent (reference example). It is a figure showing the amount of peracetyl γCD dissolved in a solvent (reference example). It is the figure which showed the test result of the marine organism adhesion prevention test (test example 2).

Explanation of symbols

(A) Location where anti-adhesive agent is applied (b) Location where mussel is fixed (c) Number of tentacles extended

Claims (5)

  An anti-adhesion agent for marine organisms, wherein a biological repellent component is included with a water-insoluble cyclodextrin (CD) or a sparingly water-soluble cyclodextrin (CD).   The marine organism adhesion inhibitor according to claim 1, wherein the water-insoluble cyclodextrin (CD) or the sparingly water-soluble cyclodextrin (CD) is a peracylated cyclodextrin (CD).   The anti-adhesion agent for marine organisms according to claim 1 or 2, wherein the organism-derived repellent component is derived from a plant.   4. The marine organism adhesion inhibitor according to claim 3, wherein the biological repellent component is allyl isothiocyanate (AITC).   Use of the adhesion preventing agent for marine organisms according to any one of claims 1 to 4.