WO2006090719A1

WO2006090719A1 - Agent and method for preventing attachment of marine organism

Info

Publication number: WO2006090719A1
Application number: PCT/JP2006/303127
Authority: WO
Inventors: Jian Ping Gong; Yoshihito Osada
Original assignee: National University Corporation Hokkaido University
Priority date: 2005-02-22
Filing date: 2006-02-22
Publication date: 2006-08-31
Also published as: JPWO2006090719A1

Abstract

A marine organism attachment preventive agent which comprises, as a main component, a multi-functional water-soluble polymer having an ion-crosslinkable group as a functional group, and can form a hydrogel film of the above water-soluble polymer on the surface of an article to be exposed to the marine circumstance, when it is applied to the surface of the above article in the form of an aqueous solution and then is ion-crosslinked. Further, a method for preventing the attachment of a marine organism to an article to be exposed to the marine circumstance, which comprises a first step of applying an aqueous solution containing, as a main component, a multi-functional water-soluble polymer having an ion-crosslinkable group as a functional group on the surface of the above article, to form a coating film of the above aqueous solution, an optional second step of drying the above coating film to form a coating film of the above water-soluble polymer, and, a third step of applying an aqueous solution containing a multi-valent metal ion, such as sea water, to the above coating film of the aqueous solution or the above coating film of the water-soluble polymer formed on the surface of the above article, to thereby subject the water-soluble polymer to the ion-crosslinking and form a hydrogel film on the surface of the above article.

Description

Specification

Marine organism adhesion inhibitor and method thereof

Technical field

[0001] The present invention is a marine organism adhesion prevention capable of effectively preventing marine organisms from adhering to an object (for example, fish net, bottom net, nuclear power plant intake, ship bottom) disposed in the marine environment. It relates to the agent.

Background art

[0002] Currently, drugs called antifouling agents (anti-adhesive agents) are applied to fishing nets and ship bottoms in order to prevent fouling organisms from attaching. This drug is composed mainly of organic nitrogen sulfur or inorganic copper compounds that have a herbicidal effect, and when it is immersed in seawater, it gradually dissolves and exhibits a herbicidal effect. In other words, this means that it also has an indiscriminate effect on edible marine products such as kombu and useful seaweed that live near the surface such as nets. As a result, many malformations in which male reproductive organs appear in female shellfish have been found throughout the coast of Japan. In recent years, this antifouling agent has been continuously improved in consideration of its low impact on the environment and its long-lasting effect, but in order to be relatively resistant to poisons and effective against shellfish, A certain amount of high toxicity is still necessary. However, the use of controlled-release antifouling agents that cause marine pollution should be permanently banned as a result of the enormous impact on the ecosystem.

[0003] Therefore, the present inventors have studied antifouling treatment technology that does not affect the ecosystem and the natural environment, replacing the conventional antifouling agent. And obtained a patent application for the result (Patent Document 1) Patent Document 1: WO03 / 067990

Disclosure of the invention

Problems to be solved by the invention

[0004] However, as a result of subsequent studies by the present inventors, although the Hyde Mouth Gel itself has an effect of preventing the adhesion of marine organisms, it has an adhesive strength that can withstand even in an actual field (underwater). In fact, it was found that it was extremely difficult to attach the id gel to the surface of the object to be applied. In particular, in order to ensure the effect of preventing the adhesion of marine organisms over the medium to long term, it is necessary to attach a certain degree of hyde mouth gel to the surface. As described below, it was extremely difficult.

[0005] First, the present inventors tried various methods for preparing a hide-mouthed gel and bonding the gel to the surface of an object to be applied. However, in addition to being difficult to adhere with satisfactory strength in any of the methods, even if it can be bonded with sufficient strength, in the case of an application object having a complicated shape, Another problem is that coating is very difficult. In this way, the water-containing gel is adhered to the surface of the object to be applied, and the gel of a certain thickness is adhered to the surface of the object to be complicatedly shaped. It was concluded that it was extremely difficult to bond with sufficient strength to maintain the adhesive state.

[0006] Therefore, the present inventors examined a method of polymerizing and cross-linking after applying a monomer solution such as acrylic acid to the surface of the object to be applied as the next method. However, for example, when radical polymerization is performed in the field (outdoor) according to the method described in Example 1 of Patent Document 1 (acrylic acid as a monomer, methylene bisacrylamide as a crosslinking agent, and potassium persulfate as a polymerization initiator). As a result, the radical reaction was inhibited by oxygen in the air, and as a result, a satisfactory gel could not be formed on the surface of the object to be applied. Here, in radical polymerization, there are a method of heating at 60 ° C or higher for several hours and a method of irradiating with ultraviolet light (UV). It is neither technically easy nor practical to apply to.

[0007] As a result of the present inventors' tests, it has been found that the technique of applying a monomer solution tends to form a sea-island during the drying process. When it becomes a sea-island shape, a uniform layer cannot be formed, and the formed thin gel cannot easily be peeled to a desired gel thickness. In the case of a technique such as the monomer aqueous solution of Example 4 below, it was found that the monomer itself diffuses into the solution, so that even a thin gel cannot be formed.

[0008] Furthermore, in actual use, if the monomer solution is applied to the surface of the object to be applied and then a time is passed until the polymerization / crosslinking step, the liquid may be partially dried. Assumption (For example, summer). In this case, in order to polymerize the monomers, the molecules must collide with each other. Therefore, a high monomer concentration and monomer mobility are required for the reaction. The gel does not progress and falls into a state where no gel is formed.

[0009] Furthermore, in the method of applying the monomer to the surface of the object to be applied, some unreacted monomer remains, but since the monomer is generally harmful to living organisms, it adversely affects the surrounding marine environment. Effect.

[0010] Therefore, the present invention can fix a hyde mouth gel effective for preventing marine organism adhesion to the surface of an object to be applied with a simple and sufficient adhesive strength, and can easily adjust the gel thickness. The purpose of the present invention is to provide an extremely practical marine organism adhesion preventive agent that can achieve low cost and high environmental safety, and does not require special equipment or equipment.

Means for solving the problem

[0011] The present invention (1) is based on a polyfunctional water-soluble polymer having an ionic crosslinkable group as a functional group (for example, a water-soluble polymer that can be ionically cross-linked with a polyvalent metal ion to form a gel). A marine organism that is capable of forming a water-soluble polymer hydrogen film on the surface of the object by ionic crosslinking after being applied in the form of an aqueous solution to the surface of the object distributed in the marine environment. It is an anti-adhesive agent.

[0012] In the present invention (2), the water-soluble polymer may be polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly-2-acrylamide-2-methylpropanesulfonic acid (PAMPS), polyvinylphenol, Polymaleic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl metatalylate, alginic acid, dielan gum, carboxymethyl cellulose, xanthan gum, natural gum, agar, agarose, force ragenan, fucodyne, fulselaran, laminaran, ibaranoli Said invention (1), which is one or more compounds or salts selected from the group consisting of giraffe, gum arabic, gum arabic, gala rubber, tragacanth gum, locust bean gum, arabinogalatatan, pectin and amylopectin Is a marine organism anti-adhesion agent .

[0013] The present invention (3) is a method for preventing adhesion of an object placed in a marine environment by marine organisms, Applying an aqueous solution mainly composed of a polyfunctional water-soluble polymer having an ionic crosslinkable group as a functional group to the surface of the object to form a film of the aqueous solution;

A second step optionally drying said aqueous solution film to form said water-soluble polymer film; and

Applying a polyvalent metal ion-containing aqueous solution to the aqueous film or the water-soluble polymer film formed on the surface of the object, and ion-crosslinking the water-soluble polymer to form a hydrogel film on the surface of the object Third process

It is the method characterized by having.

[0014] In the present invention (4), the water-soluble polymer may be polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly-2-acrylamido-2-methylpropanesulfonic acid (PAMPS), polyvinylphenol, Polymaleic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl metatalylate, alginic acid, dielan gum, carboxymethyl cellulose, xanthan gum, natural gum, agar, agarose, force ragenan, fucodyne, fulselaran, laminaran, ibaranoli Said invention (3) which is one or more compounds or salts selected from the group consisting of giraffe, gum arabic, gum arabic, gala rubber, tragacanth rubber, locust bean gum, arabinogalatatan, pectin and amylopectin This is the method.

[0015] The present invention (5) is the method of the above invention (3) or (4), wherein the polyvalent metal ion-containing aqueous solution is seawater.

[0016] In the present invention (6), in the third step, the object in which the aqueous film or the water-soluble polymer film is formed on the surface of the object is immersed in seawater. This is the method of the invention (5).

The invention's effect

[0017] According to the present invention, a hide-mouthed gel effective in preventing marine organism adhesion can be fixed to the surface of an object to be applied with a simple and sufficient adhesive strength, and the gel thickness can be easily adjusted. At the same time, it is possible to provide an extremely practical marine organism adhesion preventive agent that can achieve low cost, high environmental safety, and does not require special equipment or equipment. In addition, when such gel is applied to the bottom of a ship, the side of a ship, etc. Is more effective because it has the effect of reducing frictional resistance (see Japanese Patent Application 2001-13617). In addition, the non-use of expendable drugs is expected to reduce the financial burden on fishery workers.

Brief Description of Drawings

[Figure 1] Figures 1 (a) to 1 (d) show test solution 1 applied sample 1 (a), test solution 2 applied sample 1 (b), test solution 3 applied sample 1 (c) at the initial stage of the outdoor test. As a control, the surface condition of the test solution non-applied block (d) is shown.

[Figure 2] Figures 2 (a) to (d) show test solution 1 applied sample 1 (a), test solution 2 applied sample 1 (b), and test solution 3 three months after the start of the field test. It shows the surface condition of applied sample 1 (c) and control solution non-applied block (d) as a control.

[Fig. 3] Fig. 3 (a-l) to (d 2) show test solution 1 applied sample 2 (a-1 and a-2), test solution 2 applied sample 2 (b), It shows the surface state of test solution 3 applied sample 2 (c) and, as a control, a block with expanded metal with no test solution applied (d-1 and d-2).

[Fig.4] Fig.4 (& 1) to ((1 2) shows test solution 1 applied sample 2 (a-1 and a-2), test solution 2 applied one month after starting outdoor test. The surface condition of Sample 2 (b), Test Solution 3 applied sample 2 (c), and a block with expanded metal (d-1 and d-2) without test solution as a control is shown.

[Fig. 5] Fig. 5 (& —1) to ( ₍ : -2) are test solution 1 applied sample 2 (a-1 and a-2), test solution 3 months after starting outdoor test. 2 shows the surface conditions of sample 2 (b 1 and b-2) and test solution 3 sample 2 (c-1 and c 2).

[Fig. 6] Fig. 6 (& —1) to ( ₍ : -2) shows test solution 1 applied sample 2 (a-1 and a-2), test solution 4 months after starting outdoor test. It shows the surface condition of 2 sample 2 (b 1 and b-2) and test solution 3 sample 2 (c-1 and c 2).

[FIG. 7] FIG. 7 shows the state of the metal disk surface coated with the polymer once according to Example 4 (in the figure, the region A is a gel region and the region B is untreated). Area).

[FIG. 8] FIG. 8 shows the state of the surface of the metal plate coated with the polymer three times according to Example 4 (in the figure, the region A is the gel region and the region B is untreated). Area). [Fig. 9] Fig. 9 shows the state of the surface of the metal disk coated with a single monomer according to Example 4 (in the figure, the region A is the gel region and the region B is untreated). Area).

[FIG. 10] FIG. 10 shows a state of the surface of the metal disk coated with a single polymer according to Example 5 (in the figure, the area A is the application area and the area B is the untreated area). Is).

[FIG. 11] FIG. 11 shows the state of the surface of a metal plate coated with a polymer three times according to Example 5 (in the figure, the area A is the application area, and the area B is the untreated area). Is).

BEST MODE FOR CARRYING OUT THE INVENTION

[0019] First, the marine organism adhesion inhibitor according to the present invention will be described. This marine organism adhesion inhibitor is characterized by containing a polyfunctional water-soluble polymer having an ionic crosslinkable group as a functional group as a main component. Hereinafter, first, the water-soluble polymer will be described in detail.

First, the “ionic crosslinkable group” of the water-soluble polymer means that the ion crosslinkable groups are multivalent metal ions {for example, divalent and trivalent metal ions (for example, Mg ²⁺ , Ca ²⁺ , Cu ^2+, Zn ² +, although Fe ³⁺⁾ is not particularly limited as long as ionic crosslinking group capable of being in}, when performing I O emissions crosslinked using seawater, seawater pH (e.g., 8-8 It is preferred that the group is ionized or ionizable in 5). Examples of such a group include a carboxyl group, a hydroxyl group, a sulfonic acid group, and a phosphoric acid group. In addition to the “ionic crosslinkable group”, it may have a functional group (for example, amine or OH group) capable of coordinating with a metal ion. In addition, “water-soluble” means that 0.01% by mass (wt%) or more dissolves in water at 25 ° C. Furthermore, the water-soluble polymer may or may not have a functional group other than the ion crosslinkable group.

[0021] Next, preferred examples of the water-soluble polymer will be given. First, the first group is a homopolymer or copolymer having an unsaturated organic acid as an essential component and an unsaturated compound as an optional component, or a salt thereof. Here, examples of unsaturated organic acids as essential components include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, oleic acid, itaconic acid, cinnamic acid, propiolic acid; Unsaturated acids having a hydroxyl group bonded to the aromatic ring of, for example, vinylphenol; unsaturated sulfonic acids, for example, 2-methyl group pen senorephonic acid, vinylolacenorephonic acid, arinolacenorephonic acid, Nonsulphonic acid, a methyl styrene sulfonic acid; unsaturated phosphoric acid such as burric acid, phosphate s Tell. An example of an unsaturated compound as an optional component is acrylamide. Specifically, for example, polyacrylic acid (PAA), polymethacrylic acid (PMAA), poly-2-acrylamide-2-methylpropanesulfonic acid (PAMPS), polybufenol or polymaleic acid or a salt thereof (for example, sodium salt) It is. Next, the second group is a homopolymer or copolymer of an unsaturated carboxylic acid ester having a hydroxyl group as a bridging group, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate. It is a coalescence. Next, the third group consists of ionic polysaccharides such as alginate, dielan gum, carboxymethylcellulose, xanthan gum, natural gum, agar, agarose, force laganin, fucodyne, flucellaran, laminaran, ibaranori, giraffe, gum arabic, gum Chigum, Karaa gum, tragacanth gum, locust bean gum, arabinogalatatan, pectin and amylopectin.

Here, the water-soluble polymer according to the present invention may be a synthetic polymer or a natural polymer, as can be seen from the above examples. Here, the water-soluble polymer is preferably a polymer having a polymerization degree of 1000 or more. For example, polyacrylic acid is not particularly limited in terms of its molecular weight, linear or branched shape, etc. For example, the weight average molecular weight (Mw) force in terms of polystyrene is usually from 0,000 to 1, About 500,000.

[0023] The water-soluble polymer can be produced by a well-known method and is also sold. For example, as a commercial product of polyacrylic acid, for example, Viscomate (registered trademark) series manufactured by Showa Denko KK (for example, NP-600, NP-700, NP-800; SL-104Y as partially neutralized products) , Aquaric (registered trademark) L and H series manufactured by Nippon Shokubai Co., Ltd., and Jurimer (trademark) series manufactured by Nippon Pure Chemical Co., Ltd.

[0024] Since the constituent components of the present inhibitor have been described above, the present inhibitor, which is a composition, will be described. First, the present inhibitor contains the water-soluble polymer as a main component. Here, the “main component” means that the component occupies a majority (for example, weight) in the entire composition (dried product). The composition is used in the form of an aqueous solution at the time of use. At this time, if the blending amount of the water-soluble polymer is too small, the viscosity becomes small, so that a sufficiently thick film may not be formed. On the other hand, if the blending amount of the water-soluble polymer is too large, the viscosity It is assumed that the workability will deteriorate because of the increase of did Therefore, the blending amount is appropriately determined so as to obtain a suitable viscosity in accordance with the type and molecular weight of the polymer to be used. Here, the viscosity (dynamic viscosity) is preferably lOPa's or more. The upper limit is not particularly limited, but is, for example, 10 ⁷ Pa's or less. A more preferred viscosity range is 10 ² to 10 ⁶ Pa's. Measurement conditions refer to values measured with a rotary rheometer (ARES-lOOFRTNl) under specified conditions (temperature: 27.0 ° C, Frequency: 0.01 rad / s, Strain: 1%). The content of the water-soluble polymer is not particularly limited. For example, when the water-soluble polymer is polyacrylic acid, it is 10% by weight or more based on the total weight (more preferably 20 to 50). % By weight) is preferred.

[0025] It should be noted that the marine organism adhesion inhibitor according to the present invention is a force in the form of an aqueous solution as described above when used, and is not limited to this. And types that are concentrated and diluted with water during use. The “aqueous solution” in this specification is not limited to the case where the water-soluble polymer is completely dissolved, but also includes the case where the water-soluble polymer is partially dispersed (that is, the portion is not completely dissolved).

[0026] Here, the "marine organism" in the present invention is not particularly limited as long as it is a plant inhabiting the ocean. For example, marine plants such as kombu, barnacles, Kasane Kanzashi, Murasakigi, sea squirt, etc. List marine animals.

[0027] The term "object distributed in the marine environment", which is the object of adhesion prevention, means any object that is distributed in the marine environment. For example, an object that is submerged in seawater or is present in the vicinity of seawater. For example, underwater structures such as boats (especially ship bottoms), seawater intake channels, wave-dissipating blocks, drainage channels, tetrapots, aquaculture nets, buoys and stationary nets, etc. And marine facilities. In addition, objects placed in a simulated marine environment (including aquarium itself) such as aquariums and live aquariums also fall under “objects placed in the marine environment”.

[0028] Next, a method of using the marine organism adhesion inhibitor according to the present invention (a method of forming a hyde mouth gel on an object placed in the marine environment) will be described. First, when the present marine organism adhesion inhibitor is in a dry form or a concentrated form, an aqueous polymer solution having a suitable viscosity is prepared by adding a predetermined amount of water (step 0).

[0029] Here, before applying the object to the polymer aqueous solution, for example, polyvalent metal ion water The polymer in the polymer aqueous solution may be incompletely (weakly) ion-crosslinked by adding a solution (step 0, step 2). In this case, the equivalent of the polyvalent metal ion to be added is set to be smaller than the equivalent of the ionic crosslinking group of the polymer existing in the system. At this time, a part or all of the polyvalent metal ion aqueous solution may be seawater.

[0030] Next, an aqueous polymer solution (in some cases, a weakly ion-crosslinked polymer aqueous solution) is applied to the material (first step). Here, examples of the application method include a method of immersing the object in an aqueous polymer solution, a method of applying the object to the object with a brush, and a method of spraying the object by spraying. Here, as for the application thickness, when a polymer aqueous solution is used as in the present invention, it is usually possible to construct a thickness of several nanometers to several micrometers per application.

[0031] Next, in some cases, the object to which the polymer aqueous solution is applied may be dried (second step). The drying conditions are not particularly limited, and examples thereof include an aspect in which the drying conditions are left for several days at an outside temperature. In addition, when the object is submerged in seawater in the third step, the effect of dripping the polymer aqueous solution can be prevented and the polymer aqueous solution adheres to a person or a carrier. This is convenient for handling.

[0032] Next, an ionic cross-linking agent is applied to the film-forming object (the object on which the aqueous polymer film or the water-soluble polymer film is formed). Here, the ionic crosslinking agent, as described above, multivalent (e.g., divalent, trivalent) cation ^{^{(e.g., Mg 2+, Ca 2 +,}} Cu 2+, Zn 2+, Fe 3+) is Fe ³⁺ is more preferable from the viewpoint of making the formed hydrated gel high strength. For example, Fe (SO), FeCl, CaCl and MgCl

2 4 3 3 2 2 Aqueous solution can be used. In this case, the amount of the ionic cross-linking agent is preferably an equivalent amount sufficient for ionic cross-linking of the ionic cross-linkable group present in the system. For example, 20 to 50% by weight of an aqueous polyacrylic acid solution is added. when using the preferred concentration of Fe ³⁺ aqueous solution is at 1 X 10 ^_3 M or more, more preferably in ^{^{5 X 10 _3 M~1 X 10 _1}} M. For Ca ²⁺ and Mg ² +, preferably the concentration in the aqueous solution is at least 1M, more preferably 1M～: a L0M.

[0033] However, in practice, these polyvalent metal ions (trivalent cations such as Fe ³⁺ , Mg ²⁺ , C It is advantageous to use seawater containing divalent cations such as a2 ⁺ , Cu2 ⁺ and Zn2 ⁺ . That is, the ability to sink the film-forming object into the sea By spraying seawater on the object, the polymer is ionically crosslinked, resulting in the formation of a hide mouth gel that exhibits the effect of preventing marine organism adhesion.

[0034] Here, as described above, a hyde-mouth gel having a thickness of several nanometers and a thickness of several nanometers is usually formed by a single operation (the above-mentioned first process force up to the third process). Is possible. However, if it is necessary to form a thicker mouth-mouthed gel (e.g., several tens of micrometers, millimeters), e.g. to ensure long-term durability, the above operation is repeated many times. The thickness of the water-soluble polymer can be adjusted as appropriate by increasing the viscosity of the water-soluble polymer by repeating the treatment or increasing the concentration of the water-soluble polymer or increasing the molecular weight.

[0035] Next, the hide mouth gel formed through the above-described operation is preferably a hide mouth gel having a swelling degree of 1.5 to 500, and particularly preferably a swelling degree of 2 to: LOO Hyde mouth gel. Here, the degree of swelling refers to a value obtained by dividing the sum of the weight of water and the weight of polymer in the hydrated gel by the weight of the polymer.

[0036] It is preferable that the formed hide-mouthed gel is capable of releasing protons. More specifically, (and most ^{preferably, 10- 2 mol / L~ lmol /} L) proton concentration force 10- ⁶ mol / L~5mol / L is preferably those which are. Here, the proton concentration in the hyde mouth gel can be determined according to the method described in Macromol. Rapid Commun. 16, 713-716 (1995). Here, the “proton concentration” is a value obtained by dividing the number of moles of protons originally held by the water-soluble polymer by the volume of the hydose mouth gel, that is, the number of moles of protons dissociated from the water-soluble polymer column. And the number of moles of undissociated protons still bound to the water-soluble polymer divided by the volume of the gel.

Example

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to the following examples.

Use concrete blocks and concrete blocks with expanded metal as objects. It was. First, a concrete block and a concrete block with expanded metal were immersed in a PAA aqueous solution (35 wt% aqueous solution, Aldrich, weight average molecular weight 250, 000, dynamic viscosity: 1.02 X 10 ⁶ Pa-s). . After that, pull out the concrete block and the expanded concrete block with PAA aqueous solution, and then immerse it in CaCl aqueous solution (1.9 M).

2

By soaking, a white PAA nose mouth gel was formed on the concrete block and the concrete block with expanded metal. CaCl aqueous solution (2.5M) and MgCl water

Even when 2 2 solution (1.0M, 1.4M) is used instead of CaCl aqueous solution (1.9M)

2

A white PAA nodrogel was formed on the concrete block and the concrete block with expanded metal.

[0039] i m)

Concrete objects and concrete blocks with expanded metal were used as objects. First, a concrete block and a concrete block with expanded metal were immersed in a PAA aqueous solution (35 wt% aqueous solution, Aldrich, weight average molecular weight 250, 000, dynamic viscosity: 1.02 X 10 ⁶ Pa-s). . After that, the PAA aqueous solution force also pulled out the concrete block and the concrete block with expanded metal, followed by Fe (SO) aqueous solution (4.4 X 10

2 4 3

^_3 M), a reddish PAA Hyde Mouth Gel was formed on the concrete block and the concrete block with expanded metal. In addition, Fe (SO) aqueous solution (

2 4 3

1. When using 75 X 10 ^_2 M), a reddish PAA nod mouth gel was formed on the concrete block and the concrete block with expanded metal.

[0040] Example 3 (field test, test example)

Using a mixed solution obtained by mixing PAA aqueous solution (35% by weight) and seawater at a specified volume ratio as an anti-adhesive agent, and using concrete blocks and concrete blocks with expanded metal as objects, The test was conducted.

[0041] First, a PAA aqueous solution (35 wt%, manufactured by Ardrich, weight average molecular weight 250, 000, dynamic viscosity: 1.02 X 10 ⁶ Pa's) was used as a concentrated solution. The diluted solution (test solution) was prepared by mixing this concentrated solution with seawater at a predetermined volume ratio (concentrated solution: seawater = 2: 1, dynamic viscosity: 6.5 X 10 ⁴ Pa ' s). Next, sample 1 (concrete block tied with rope) and sample 2 (concrete block with expanded metal tied with rope). For rock, both samples were immersed in the test solution and then dried (repeated 3 times). Thereafter, Sample 1, Sample 2 and the control (no test solution applied) were submerged in sea water for a predetermined period (3 months for sample 1 and control; 4 months for sample 2 and control). Figures 1 (a) and (b) are photographs of sample 1 (test solution applied) and control (no test solution applied), respectively, at the start of the test. Figures 2 (a) and (b) are photographs of sample 1 (test solution applied) and control (no test solution applied), respectively, 3 months after the start. As is clear from these photographs, the adhesion of marine organisms was almost unrecognized for Sample 1 to which the test solution was applied. On the other hand, the attachment of a large amount of marine organisms (mainly barnacles) was confirmed for the control.

Next, FIGS. 3 (a-1) to (b-2) are photographs of sample 2 (test solution applied) and control (no test solution applied) at the start of the test, respectively. Figures 4 (a-l) to (b-2) are photographs of sample 2 (test solution applied) and control (no test solution applied) one month after the start, respectively. Here, a large amount of marine organisms (mainly barnacles) were attached to the control at this stage, making it impossible to continue the test any further. Figures 5 (a-l) to (a-2) are photographs of sample 2 to which the test solution was applied, 3 months after the start. Figures 6 (a-1) to (a-2) are photographs of Sample 2 to which the test solution was applied, with the starting force also after 4 months. As is clear from these photographic powers, with regard to Sample 2 to which the test solution was applied, the adhesion of marine organisms was hardly confirmed even after 4 months from the start of the test. On the other hand, regarding the control, a large amount of marine organisms (mainly barnacles) was confirmed one month after the start of the test.

[0043] Example 4 (grid peeling test)

In this example, a water-soluble polymer aqueous solution is applied and ion-crosslinked to form a hydration gel on the surface of the metal substrate, and an aqueous monomer solution constituting the polymer is applied and polymerized and ion-crosslinked. A comparative test was conducted on the peelability of the substrate when a hydose gel was formed on the surface of the metal substrate. Here, the aluminum base is used as the metal base, and the polyacrylic acid (made by Ardrich, weight average molecular weight 250, 000) as the water-soluble polymer aqueous solution is 35 wt% aqueous solution (dynamic viscosity: 1.02 X 10 ⁶ Pa 's). As a monomer aqueous solution, a 35 wt% acrylic acid aqueous solution is used. ) A 10 wt% aqueous solution was used.

[0044] Water-soluble polymer aqueous solution>

First, application (coating): (1) Apply the polymer solution with a brush on the surface of the half of the aluminum substrate, (2) Then immerse in the solution of the cross-linking agent, (3) After 5 minutes, the base from the cross-linking agent solution The procedure was pulled up and dried. A series of steps (1) to (3) that were performed once was defined as one polymer coating, and three times as a polymer three times. Here, Fig. 7 shows the appearance of an aluminum substrate with a single coating of polymer (in the figure, region A is the gel region and region B is the untreated region). Shows the appearance of the substrate (in the figure, the region A is the gel region and the region B is the untreated region). Thus, with respect to the substrate coated with the polymer, it was observed that the polymer was polymerized and gelled on the substrate where the polymer did not diffuse into the solution. Moreover, the thickness of the gel increased by repeating the work process.

First, the application (coating) is: (1) Apply the monomer solution to the surface of the half of the aluminum substrate using Kimwipe (registered trademark), (2) Then immerse in the solution of the cross-linking agent, (3) Cross-linking agent after 5 minutes The procedure was to lift the substrate from the solution and dry. A series of steps (1) to (3) performed once was defined as a single monomer coating. Here, Fig. 9 shows the appearance of an aluminum substrate coated with a single monomer (in the figure, the area A is the application area and the area B is the untreated area). Thus, on the substrate coated with the monomer, the monomer on the substrate diffused into the solution in the cross-linking agent solution, and the gelation on the substrate was extremely powerful.

[0046] Example 5 (sea 71 ^ exfoliation experiment)

A test was conducted as to how much the peel durability was in fresh seawater according to “Water-soluble polymer aqueous solution of Example 4”. Specifically, a constant temperature bath containing 3.5% salt water is set at a flow rate of about 10 cm / s and a water temperature of 27.0 ° C. Each of the aluminum substrates to which “Coating” was applied was allowed to stand for 72 hours perpendicular to the direction of flow, and then the degree of gel peeling on the substrate surface was observed. The results are shown in FIGS. Here, Fig. 10 shows the appearance of the surface of the aluminum board coated with a single polymer (in the figure, area A is the application area and area B is the untreated area. Fig. 11 shows the appearance of the aluminum disk surface with three coatings of polymer (in the figure, area A is the application area and area B is the untreated area). It is. As can be seen from these figures, it was confirmed that both “single polymer coating” and “three polymer coatings” remained as they were, although there was some peeling.

Claims

The scope of the claims

[1] A polyfunctional water-soluble polymer containing an ionic crosslinkable group as a main component is contained as a main component. A marine organism adhesion inhibitor capable of forming a water-soluble polymer gel film on the surface of the object by on-crosslinking.

[2] The water-soluble polymer may be polyacrylic acid, polymethacrylic acid, poly-2-acrylamide-2-methylpropanesulfonic acid, polybutanol, polymaleic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate. Talylate, alginic acid, dielan gum, carboxymethylcellulose, xanthan gum, natural gum, agarose, agarose, power ragenan, fucodyne, flucellaran, laminaran, ibaranori, giraffe, gum arabic, gatch gum, cara gum, tragacanth gum, locust bean gum, arapino The marine organism adhesion inhibitor according to claim 1, which is one or more compounds or salts selected from the group consisting of galactan, pectin and amylopectin.

[3] In a method for preventing adhesion of an object placed in a marine environment by marine organisms, an aqueous solution mainly composed of a polyfunctional water-soluble polymer having an ionic crosslinkable group as a functional group is applied to the surface of the object. And a first step of forming a film of the aqueous solution;

A method characterized by comprising:

[4] The water-soluble polymer may be polyacrylic acid, polymethacrylic acid, poly-2-acrylamide-2-methylpropanesulfonic acid, polybutanol, polymaleic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate. Talylate, alginic acid, dielan gum, carboxymethylcellulose, xanthan gum, natural gum, agarose, agarose, force ragenan, fucodyne, fulseraran, laminaran, ibaranori, giraffe, gum arabic, gatch gum, cara gum, tragacanth gum, locust bean gum, ara 4. The method according to claim 3, which is one or more compounds or salts selected from the group consisting of pinogalactin, pectin and amylopectin.

5. The method according to claim 3 or 4, wherein the aqueous solution containing polyvalent metal ions is seawater.

6. The method according to claim 5, wherein the third step is to immerse the object in which the aqueous solution film or the water-soluble polymer film is formed in seawater.