Material for preventing adhesion of marine organism and method for producing the same

Abstract

To provide a material for preventing adhesion of marine organisms, which has no toxicity, without imparting problematic impact on the environment, and which can be easily processed on the surface of a structure even in a work site near the installation place of the structure, and to provide a method for producing the same.SOLUTION: The material for preventing adhesion of marine organisms to a structure is configured to cover a surface of the structure with use of: a covering material obtained by combining a liquid A containing, as a main component, a urethane prepolymer having two or more isocyanate groups; and a liquid B containing, as a main component, a curing agent having two or more hydroxyl groups and / or amino groups. Therein powder of copper or copper alloy adheres to a surface of the covering material.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a material for preventing the adhesion of marine organisms to structures in contact with seawater, and a method for producing the same. [Background technology]

[0002] Conventionally, structures that come into contact with seawater have been manufactured using concrete, mortar, natural stone, metal, wood, plastic, etc., and specific examples include seawater intakes at thermal power plants and factories, piers, revetments, tetrapods, bridge piers, ship bottoms, buoys, fishing nets, etc. It is known that marine organisms such as barnacles, oysters, mussels, bryozoans, and algae attach to the surfaces of structures that come into contact with seawater.

[0003] When marine organisms attach to structures, they can cause problems such as poor water flow and blockages in the case of seawater intakes at thermal power plants and factories, and can cause problems such as reduced ship speed and poor fuel efficiency in the case of the bottom of a ship.In the case of other structures, they not only spoil the aesthetic appearance but also cause injuries to workers performing cleaning tasks.

[0004] To solve these problems, antifouling paints containing organotin compounds such as tributyltin compounds and triphenyltin compounds as antifouling ingredients are known (see, for example, Patent Document 1). However, while these organotin compounds have excellent antifouling properties, their strong toxicity has raised concerns about their impact on the environment, and their use is currently prohibited. Also known is a method for manufacturing metal products for preventing the adhesion of marine organisms, in which the surface of a heated steel plate is covered with an uncured coating of saturated polyester powder paint, copper or copper alloy powder is sprayed onto the surface to disperse and adhere it, the same saturated polyester powder paint is sprayed onto the surface, and the steel plate is then reheated (see Patent Document 2). However, the need for heating and reheating makes it difficult to carry out this manufacturing method at a work site near the installation site of the structure. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 58-180565 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-202608 Summary of the Invention [Problem to be solved by the invention]

[0006] The object of the present invention has been made in consideration of the above circumstances, and is to provide a marine organism adhesion prevention material and a method for producing the same which is non-toxic, has no adverse effect on the environment, and can be easily applied to the surface of a structure, even at a work site near the installation location of the structure. [Means for solving the problem]

[0007] The present invention provides a marine organism adhesion prevention material for structures, which is formed by coating the surface of a structure with a coating material comprising a combination of Liquid A, whose main component is a urethane prepolymer having two or more isocyanate groups, and Liquid B, whose main component is a curing agent having two or more hydroxyl groups and / or amino groups, and which is characterized in that copper or copper alloy powder is adhered to the surface of the coating material.

[0008] The amount of the copper or copper alloy powder adhering to the surface of the coating material is 0.1 to 5.0 kg / m 2 It is preferable that:

[0009] The copper alloy is preferably one of a copper-zinc alloy and a copper-tin alloy.

[0010] It is preferable that the liquid B further contains 0.1 to 15% by weight of a curing accelerator.

[0011] It is preferable that neither the liquid A nor the liquid B contains a silane coupling agent, or that at least one of the liquids contains less than 1% by weight of a silane coupling agent.

[0012] It is preferable that the structure is a concrete structure, a mortar structure, a natural stone structure, a prefabricated structure, a metal structure, a wooden structure, or a plastic structure.

[0013] The present invention also provides a method for manufacturing an anti-fouling material for a structure, which comprises spraying and coating a coating material composed of a liquid A mainly containing a urethane prepolymer having two or more isocyanate groups and a liquid B mainly containing a curing agent having two or more hydroxyl groups and / or amino groups onto the surface of the structure using a two-component mixed collision type spray. After the coating and before the coating material hardens, copper or copper alloy powder is adhered to the surface of the coating material.

[0014] It is preferable that the viscosities of the liquid A and the liquid B during the two-component mixing and collision are adjusted to be in the range of 500 mPa·s or less.

[0015] In the manufacturing method, the adhesion amount of the copper or copper alloy powder to the surface of the coating material is preferably 0.1 to 5.0 kg / m 2 Preferably, it is as follows.

[0016] In the manufacturing method, the copper alloy is preferably any one of alloys composed of a copper-zinc system or a copper-tin system.

[0017] In the manufacturing method, it is preferable that the liquid B further contains 0.1 to 15% by weight of a curing accelerator.

[0018] In the manufacturing method, it is preferable that neither the liquid A nor the liquid B contains a silane coupling agent, or at least one of them contains less than 1% by weight.

[0019] In the manufacturing method, it is preferable that the structure is a concrete structure, a mortar structure, a natural stone structure, a prefabricated structure, a metal structure, a wooden structure, or a plastic structure.

Advantages of the Invention

[0020] The present invention can provide a marine organism adhesion prevention material for coating the surfaces of structures that come into contact with seawater, such as sea-facing thermal power plants, factories, port facilities, ships, and marine facilities. The marine organism adhesion prevention material of the present invention coats the surface of a structure using a coating material composed of a combination of Liquid A, whose main component is a urethane prepolymer having two or more isocyanate groups, and Liquid B, whose main component is a curing agent having two or more hydroxyl groups and / or amino groups. The copper or copper alloy powder adhered to the surface of the coating material is effective in preventing the attachment of marine organisms such as barnacles, oysters, mussels, bryozoans, and algae. The copper or copper alloy powder is non-toxic, and the marine organism adhesion prevention material has almost no impact on the environment. Furthermore, the coating material made by combining the above-mentioned liquids A and B has the property of excellent adhesion to structures when a primer is used, and it hardens at room temperature without requiring heating above 100°C. Therefore, the marine organism adhesion prevention material can be easily produced at outdoor work sites near the installation site of the structure. [Brief description of the drawings]

[0021] [Figure 1] FIG. 1 is a diagram showing the results of a marine organism adhesion test in Examples 1 to 4 of the present invention and Comparative Examples 1 and 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] (covering material) The coating material used in the marine organism adhesion prevention material of the present invention is a coating material made of polyurethane or polyurea, which is a combination of liquid A, the main component of which is a urethane prepolymer having two or more isocyanate groups, and liquid B, the main component of which is a curing agent having two or more hydroxyl groups and / or amino groups.

[0023] As the urethane prepolymer constituting Liquid A, it can be obtained by reacting an isocyanate compound having two or more isocyanate groups in one molecule with a compound having two or more active hydrogens reactive with the isocyanate group in one molecule. Particularly, as the active hydrogen compound, a urethane prepolymer formed by combining one or two or more polyol compounds having two or more alcoholic hydroxyl groups in one molecule, such as polyether polyol, polyester polyol or other polyols, is preferable.

[0024] Examples of the isocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate; alicyclic polyisocyanates such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, norbornane diisocyanate; aromatic polyisocyanates such as aromatic diisocyanates like p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate; those obtained by carbodiimide modification or isocyanurate modification of the above polyisocyanates, etc. These can be used alone or in admixture of two or more. Among these, it is preferable to use aliphatic or alicyclic polyisocyanates from the viewpoint of discoloration resistance.

[0025] Specific examples of the polyether polyol include polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethyleneoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and the like, as well as random copolymers obtained by ring-opening polymerization of propylene oxide and / or ethylene oxide in the presence of one or more of low-molecular-weight active hydrogen compounds having two or more active hydrogens, such as diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol; triols such as glycerin, trimethylolpropane, and 1,2,6-hexanetriol; and amines such as ammonia, methylamine, ethylamine, propylamine, and butylamine.

[0026] Suitable examples of the polyester polyol include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, condensates of hydroxycarboxylic acids and polyhydric alcohols, and ring-opening polymers of lactones. Examples of the polybasic acids include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, dimerized linoleic acid, and maleic acid. Examples of the polyhydric alcohols that can be used include diols such as bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and neopentyl glycol; and triols such as glycerin, 1,1,1-trimethylolpropane, and 1,2,6-hexanetriol. More specifically, examples of such polyolefins include polyethylene adipate, polytetramethylene adipate, polyhexamethylene adipate, polytetramethylene sebacate, poly(diethylene glycol adipate), poly(hexamethylene glycol-1,6-carbonate), and polycaprolactone, which have diol components at both ends.

[0027] Examples of the other polyols include acrylic polyols, hydrogenated polybutadiene polyols, castor oil derivatives, tall oil derivatives, polymer polyols, polycarbonate polyols, etc. In addition, low molecular weight polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, and hexanediol are also preferably used.

[0028] These polyol compounds preferably have a number average molecular weight of 100 to 10,000, particularly 300 to 5,000, and can be used alone or in combination of two or more as desired.

[0029] The urethane prepolymer constituting the liquid A is obtained by reacting a polyol compound and an isocyanate compound, if necessary with heating, such that the ratio of the isocyanate groups contained in the isocyanate compound exceeds 1 mole with respect to 1 mole of the hydroxyl groups contained in the polyol compound, that is, the chemical equivalent ratio (NCO / OH) exceeds 1. Such a urethane prepolymer usually has isocyanate groups at both ends of its molecule. As the urethane prepolymer, it is more preferable from the viewpoints of workability, physical properties of the cured product, etc. to react the polyol compound and the isocyanate compound at a chemical equivalent ratio (NCO / OH) of 1.6 to 20 so that it is in a liquid state at 23°C.

[0030] The coating material used for the marine organism adhesion prevention material of the present invention can be formed by curing a curable composition containing a liquid A mainly composed of the urethane prepolymer, a liquid B mainly composed of a curing agent having two or more hydroxyl groups and / or amino groups, and other additives as required.

[0031] As the compound having two or more hydroxyl groups and / or amino groups constituting the curing agent for liquid B, a compound having a molecular weight of 18 to 10,000, preferably 30 to 5,000 is preferred. For example, polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, glycerin, trimethylolpropane, 1,2,4-trihydroxybutane, 1,2,3,4-tetrahydroxybutane, 1,2,6-trihydroxyhexane, 1,1,1-trimethylolethane, pentaerythritol, polycaprolactone, fructose, xylitol, arabitol, sorbitol and mannitol; low molecular weight amino alcohols such as ethanolamine; ammonia, hydrazine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, m-phenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltolylenediamine, 3,3'-dichloro-4,4'-diamino-diphenylmethane and other low molecular weight polyamine compounds, and polyols such as polyether polyol and polyester polyol that can be used in the preparation of the urethane prepolymer mentioned above; polyether polyamines such as polyoxyethylenediamine, polyoxypropylenediamine, polyoxybutylenediamine obtained by reacting the hydroxyl group at the polyether terminal obtained by reacting an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide or a mixture thereof with ammonia to substitute an amino group. Among these curing agents, it is preferable to use polyether polyol or polyether polyamine, but it is also possible to use polyether polyol or polyether polyamine in combination with one or more other low molecular weight polyols or low molecular weight polyamines. As these curing agents, the curing agent is added so that the active hydrogen in the low molecular weight compound is in a proportion of about 0.8 mol or more, preferably about 0.95 to 1.2 mol, per 1 mol of the isocyanate group contained in the urethane prepolymer.

[0032] In addition to the urethane prepolymer and the curing agent, additives such as a curing accelerator, a plasticizer, a solvent, a surfactant, an antioxidant, and a colorant can be blended in Liquid A and Liquid B as necessary according to a conventionally known formulation.

[0033] The curing accelerator is used to promote the reaction between the urethane prepolymer and the curing agent and shorten the curing time, thereby shortening the time required for construction. Examples of the curing accelerator include N-alkylbenzylamine, N-alkylaliphatic polyamine, triethylenediamine, N-alkylpiperazine, N-alkylmorpholine, dimorpholinodiethyl ether, organotin compounds such as tin octenoate and dibutyltin dilaurate, organic lead salts, organic zirconium salts or organic bismuth salts, aromatic carboxylic acids such as benzoic acid, phthalic acid, o-chlorobenzoic acid, and organic acids such as aliphatic carboxylic acids such as 2-ethylhexanoic acid, octylic acid, stearic acid, oleic acid, and linoleic acid. Octylic acid is preferably used because of its excellent compatibility with polyols. These can be used alone or in admixture of two or more. The curing accelerator can also be used during the preparation of the urethane prepolymer and can be utilized to efficiently produce the urethane prepolymer.

[0034] The curing accelerator is preferably contained in Liquid B. The content is preferably 0.1 to 15% by weight, more preferably 0.5 to 12% by weight, and particularly preferably 1 to 10% by weight based on 100% by weight of Liquid B. If the content is less than 0.1% by weight, the effect of promoting the reaction between the urethane prepolymer and the curing agent may not be exhibited. If the content exceeds 15% by weight, the curing time may be excessively shortened, and the coating material may cure before the structure is sufficiently coated.

[0035] Examples of the plasticizer include carboxylic acid esters such as phthalic acid esters, adipic acid esters, sebacic acid esters, azelaic acid esters, and trimellitic acid esters, as well as phosphate esters, normal paraffins, chlorinated paraffins, alkylbenzenes, and other various liquid components. These can be used alone or in combination of two or more.

[0036] The solvent is used as necessary to adjust the viscosity of the curable resin composition. As the solvent, an organic solvent that does not show reactivity with the liquid A and the liquid B can be preferably used. Although not limited to the following, examples include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, n-butyl acetate, and n-amyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane, petroleum hydrocarbon solvents such as mineral spirit, and glycol ether ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate. These solvents may be used in combination of two or more.

[0037] As the surfactant, various surfactants can be added alone or in combination of two or more according to the properties such as defoaming agents, emulsifying agents, and viscosity improvers.

[0038] The anti-aging agent is used to protect the film made of the above-described coating material from light, oxygen, heat, etc. Commonly used anti-aging agents include light stabilizers and antioxidants. Examples of light stabilizers include benzotriazole-based, benzophenone-based, benzoate-based, cyanoacrylate-based, hindered amine-based, and nickel-based compounds. Examples of antioxidants include hindered phenol-based, amine-based, sulfur-based, and phosphorus-based compounds.

[0039] In addition, since the coating material used in the present invention has excellent adhesion to the structure, it is not necessarily required to contain a silane coupling agent. However, for the purpose of further improving the adhesion, a silane coupling agent may be contained in at least one of the liquid A and the liquid B in an amount of less than 1% by weight, so that the curable composition constituting the coating material may contain the silane coupling agent in an amount of less than 1% by weight.

[0040] Examples of the silane coupling agent include isocyanate group-containing silanes, amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, vinyl type unsaturated group-containing silanes, etc. When epoxy group-containing silanes are contained, they are contained in the liquid A, and when amino group-containing silanes are blended, they are contained in the liquid B.

[0041] (Primer layer) In the method for producing the marine organism adhesion prevention material of the present invention, since the above-described coating material has excellent adhesion to the structure, it can be directly sprayed and coated on the surface of the structure. However, the coating material can also be coated on the surface of the structure through a primer layer. By forming a primer layer on the surface of the structure, the primer penetrates into the surface layer of the structure, so that the coating material can be more firmly adhered to the structure.

[0042] As the primer, a polyurethane primer or an epoxy resin primer having excellent adhesion to the film made of the above-described coating material (polyurea or polyurethane) can be preferably used. As the polyurethane primer, M Primer AJ manufactured by Mitsui Chemicals Industrial Co., Ltd. can be used. As the epoxy resin primer, E-1020 manufactured by Mitsui Chemicals Industrial Co., Ltd. can be used. When forming the primer layer on the surface of the structure, its thickness is preferably about 0.02 to 0.4 mm.

[0043] (Coating method on the structure) In the present invention, Liquid A, which is mainly composed of the above-mentioned urethane prepolymer having two or more isocyanate groups, and Liquid B, which is mainly composed of a curing agent having two or more hydroxyl groups and / or amino groups, are sprayed onto the surface of a structure using a two-liquid mixing collision sprayer, and it is important that the liquid pressures of Liquid A and Liquid B when mixing and colliding the two liquids are adjusted to a range of 500 psi or more and 1200 psi or less, preferably 500 psi or more and 1050 psi or less. That is, if the liquid pressure is lower than the above range, the coating properties will be poor and a uniform film will not be formed, while if the liquid pressure is higher than the above range, air bubbles will be trapped.

[0044] The spray equipment used to spray the coating material onto structures can be any spray equipment consisting of a pressure and temperature regulating metering device, a spray gun equipped with a mix chamber, and a hot hose that can be heated. In the present invention, it is important to use a two-liquid mixed impingement type spray gun.

[0045] In this two-liquid mixing impingement spray, it is preferable to select a mix chamber suitable for mixing and impinging liquid A and liquid B at a liquid pressure within the above range. In the present invention, a two-liquid mixing impingement spray gun equipped with a mix chamber having a chamber size equivalent to Graco mix chambers such as No. 000 (orifice diameter 0.020 inch), No. 00 (0.029 inch), No. 01 (0.042 inch), and No. 02 (0.052 inch) can be preferably used, although this is not limited thereto. In particular, it is preferable to use a mix chamber equivalent to the low-discharge No. 01 (0.042 inch) or the even smaller No. 00 (0.29 inch) or the like.

[0046] In the present invention, when liquids A and B are mixed and collided, specifically when liquids A and B are introduced into the mix chamber, the viscosity of each is preferably 500 mPa·s or less, and more preferably 350 mPa·s or less. If the viscosity is higher than the above range, the coating properties become poor and it becomes difficult to form a uniform coating. Adjusting the viscosity of liquids A and B to be lower reduces the difference in viscosity between the two liquids, making mixing easier and improving the physical properties of the coating.

[0047] Furthermore, as will be described later in the Examples, liquids A and B are preferably prepared so that the tack-dry time of the material after mixing and colliding liquids A and B is in the range of 10 seconds to 60 minutes, more preferably 3 to 30 minutes. The material is liquid immediately after mixing and colliding liquids A and B, but gels over time, becomes tack-dry, and then hardens into a coating material. It is desirable to adhere copper or copper alloy powder to the surface of the coating material before gelation, but it is possible to adhere copper or copper alloy powder to the surface of the coating material before it becomes tack-dry. After it becomes tack-dry, it becomes difficult to adhere copper or copper alloy powder to the surface of the coating material. If the dry-to-touch time is less than 10 seconds, it will be difficult to adhere the copper or copper alloy powder to the surface of the coating material. If the dry-to-touch time is longer than 60 minutes, there is a possibility that a large proportion of the copper or copper alloy powder will settle inside the coating material. Furthermore, if the work is done outdoors, dirt and dust such as sand and dust may adhere to the surface of the coating material, which may prevent the coating material from achieving its function and effectiveness in preventing the adhesion of marine organisms.

[0048] In the present invention, in order to form a uniform coating, in addition to the liquid pressure when the liquid A and liquid B are mixed and collided, the viscosities of liquid A and liquid B, the discharge direction (upward, downward, horizontal direction), the spray distance which is the distance between the discharge port of the two-liquid mixing and colliding type spray and the surface of the structure, etc., it is desirable to appropriately adjust various conditions. For example, when the discharge direction of the spray is the horizontal direction, it is preferable that the spray distance is in the range of 20 to 100 cm, and more preferably 30 to 80 cm. If it is less than 20 cm, the discharge of the spray will be locally concentrated and uneven thickness is likely to occur. If it exceeds 100 cm, in the case of a material with fast curing, a large amount of mist will be generated or there will be a locally particle-like cured part, which will inhibit the formation of the coating and reduce the physical properties of the coating material.

[0049] In the method for manufacturing the marine organism adhesion prevention material of the present invention, as described above, directly on the surface of the structure, or when the above-mentioned primer layer is formed, on the primer layer, by using a two-liquid mixing and colliding type spray, a coating material composed of liquid A and liquid B is applied. The coating preferably has a thickness of 0.5 to 3 mm, particularly 0.7 to 2.5 mm. If the thickness of the coating is thinner than the above range, there is a possibility that it may not exhibit a sufficient function as a protective coating. On the other hand, if it is thicker than the above range, it will be inferior in terms of economy. When spraying the coating material, since the coating amount per reciprocation of the spray gun varies depending on the liquid pressure, liquid viscosity, orifice diameter of the mixing chamber, etc., it is desirable to adjust the coating amount while checking the state of the sprayed coating material. Particularly for materials with slow curing, although it is advantageous in that the air bubbles entrained during spraying are likely to escape, if a large amount is sprayed at once, liquid dripping may occur and the target coating thickness may not be obtained, so it is necessary to spray in small amounts in several times.

[0050] The coating formed by the method for manufacturing the marine organism adhesion prevention material of the present invention has a tensile strength of 2.3 N / mm 2 or more and an elongation at break of 200% or more, and can be formed as a coating that follows the displacement of the structure and withstands the corresponding stress.

[0051] (copper or copper alloy powder adhesion) The copper or copper alloy powder used in the marine organism adhesion prevention material of the present invention adheres to the surface of a coating material, thereby preventing the adhesion of marine organisms. Copper alloys contain alloying elements in addition to copper, which gives them properties such as superior corrosion resistance compared to copper. The alloying elements are preferably at least one of zinc, tin, nickel, and manganese, more preferably at least one of zinc and tin, and particularly preferably either a copper-zinc or copper-tin alloy. The copper / alloying element weight ratio is preferably 97 / 3 to 50 / 50, more preferably 90 / 10 to 55 / 45, and particularly preferably 80 / 20 to 60 / 40. If the alloying element ratio is less than 97 / 3, the alloy will be almost identical to copper, making it difficult to achieve excellent corrosion resistance. If the alloying element ratio is more than 50 / 50, the effect of preventing the adhesion of marine organisms may be weakened.

[0052] The copper or copper alloy powder preferably has a particle size of 10 to 500 μm, more preferably 15 to 300 μm, and particularly preferably 20 to 200 μm. If the particle size is less than 10 μm, the powder may be stirred up by the air current, making it difficult to adhere to the surface of the coating material. If the particle size is more than 500 μm, the powder may peel off from the surface of the coating material, and the effect of preventing adhesion of marine organisms may not be obtained.

[0053] The copper or copper alloy powder is applied to the surface of the coating material in an amount of 0.1 to 5.0 kg / m 2 It is preferable to use it at a coating weight of 0.5 to 3.0 kg / m 2 It is more preferable to use it at a coating weight of 0.1 kg / m. 2 If it is less than 5.0 kg / m, it may be difficult to prevent marine organisms from attaching to the surface. 2 If the thickness exceeds this value, there is no change in the effect of preventing adhesion of marine organisms, and the production cost may simply increase.

[0054] The powder of the copper or copper alloy is adhered to the surface of the coating material after coating the surface of the structural material with the coating material composed of a combination of Liquid A and Liquid B and before curing. Regarding the adhesion method, it may be sprayed using compressed air, or it may be evenly dispersed and adhered manually using an instrument having an appropriate mesh shape such as a dustpan or a sieve. Further, it may be adhered separately from Liquid A and Liquid B using a spray gun different from the spray gun used for Liquid A and Liquid B.

[0055] When the powder of the copper or copper alloy is blended with at least one of Liquid A and Liquid B, the powder is evenly dispersed inside the coating material, and the amount of powder exposed on the surface of the coating material decreases. Therefore, in order to exert the effect of preventing the adhesion of marine organisms, it is necessary to blend a large amount of the powder, which increases the manufacturing cost. However, by adhering to the surface of the coating material, the powder can exert the effect with a small amount, and it is possible to suppress the manufacturing cost.

[0056] (Structure) The structure to which the marine organism adhesion prevention material of the present invention is applied is a structure in contact with seawater and is manufactured using concrete, mortar, natural stone, metal, wood, plastic, etc. The structure is preferably a concrete structure, a mortar structure, a natural stone structure, a composite structure, a metal structure, a wooden structure, or a plastic structure, more preferably a concrete structure, a mortar structure, a natural stone structure, or a composite structure, and particularly preferably a concrete structure or a mortar structure.

Example

[0057] Hereinafter, examples for carrying out the present invention will be described. Note that the present invention is not limited to these examples.

[0058] (Example 1) According to the following procedures (1) to (5), a coating material composed of a liquid A mainly composed of a urethane prepolymer having two or more isocyanate groups and a liquid B mainly composed of a curing agent having two or more hydroxyl groups and / or amino groups is combined and applied to the surface of a structure. After spraying a copper alloy on the surface of the coating material before the coating material cures, the coating material is cured at room temperature to form a marine organism adhesion prevention material. (1) Mortar specimens (mortar using ISO standard sand in JIS R 5201, flat plate shape of 100 mm × 100 mm × 10 mm) were prepared and surface treatment (sanding) was carried out. (2) As a primer on the specimen surface, a polyurethane primer (M Primer AJ manufactured by Mitsui Chemicals Industrial Co., Ltd.) was applied at a coating amount of 0.2 kg / m 2 . (3) The following liquid A and liquid B were used. Liquid A: AJ-800A manufactured by Mitsui Chemicals Industrial Co., Ltd. Liquid B: AJ-800R manufactured by Mitsui Chemicals Industrial Co., Ltd. (4) Using liquid A which is a polyisocyanate prepolymer and liquid B which is a diamine curing agent, liquid A and liquid B were heated to a viscosity of 100 - 150 mPa·s respectively. As a two-liquid impact mixing type spray machine, a spray device H-VR manufactured by Graco was used, and a probe gun manufactured by Glass Craft (using the company's mixing chamber No. 00) was attached and used. The coating material was sprayed from above at a spray distance of about 60 cm so that the thickness of the coating material on the horizontally placed specimen surface was about 2 mm. The gel time of the above coating material was 90 seconds and the touch-dry time was 1200 seconds (20 minutes). (5) Within 90 seconds from the end of the spraying in (4) until the gel time, using a tea strainer, copper-zinc alloy (copper / zinc = 70 / 30) particles with a particle size of 150 μm were sprayed on the surface of the coating material at an adhesion amount of 900 g / m 2 . Then, it was left to cure at room temperature for 24 hours or more to produce a marine organism adhesion prevention material. The marine organism adhesion prevention material on this specimen was taken as Example 1. The above coating conditions are shown in Table 1.

[0059] Here, for the gel time and finger-touch drying time, the evaluation method conforms to JIS K-5600-1-1 etc. After continuously spraying the coating material onto the surface of the vertically standing test piece from a distance of 60 cm for 2 seconds, the time until the dripping of the sprayed coating material stops was measured as the gel time. Also, after continuously spraying the coating material onto the surface of the horizontally placed test piece from a distance of 60 cm for 2 seconds, the center of the surface of the sprayed coating material was gently touched with a fingertip, and the time until the fingertip was not soiled was measured as the finger-touch drying time.

[0060] (Example 2) In Example 2, in the above (5), an anti-fouling material for marine organisms was produced in the same manner as in Example 1, except that copper-tin alloy (copper / tin = 90 / 10) particles with a particle size of 50 μm were used instead of copper-zinc alloy particles with a particle size of 150 μm. The above coating conditions are shown in Table 1.

[0061] (Example 3) In Example 3, in the above (5), an anti-fouling material for marine organisms was produced in the same manner as in Example 1, except that copper-tin alloy (copper / tin = 67 / 33) particles with a particle size of 23 μm and an adhesion amount of 600 g / m 2 were used instead of copper-zinc alloy particles with a particle size of 150 μm and an adhesion amount of 900 g / m 2 . The above coating conditions are shown in Table 1.

[0062] (Example 4) In Example 4, in the above (4), a diamine curing agent in which 8 parts by weight (7.3% by weight) of octylic acid was added as a curing accelerator was used for the liquid B, and in the above (5), an adhesion amount of 200 g / m 2 was used instead of an adhesion amount of 600 g / m 2 . An anti-fouling material for marine organisms was produced in the same manner as in Example 3. Here, for the coating material at room temperature after spraying was completed by spray, the gel time was 20 seconds and the finger-touch drying time was 300 seconds (5 minutes). The above coating conditions are shown in Table 1.

[0063] (Comparative Examples 1 - 2) In Comparative Example 1, except for omitting the above (5), a marine organism adhesion prevention material was produced in the same manner as in Example 1. The above application conditions are shown in Table 1. In Comparative Example 2, a marine organism adhesion prevention material was produced in the same manner as in Example 1, except that the above steps (2) to (5) were omitted. The above application conditions are shown in Table 1.

[0064] [Table 1]

[0065] (Marine biofouling test) Mortar specimens with seven different surface conditions, Examples 1 to 5 and Comparative Examples 1 and 2, were each fixed to a protective frame, hung along the quay of the port in Matogata-cho, Himeji City, Hyogo Prefecture, and immersed in the sea. A marine organism adhesion test was conducted by exposure to the sea for three months from June to September 2023.

[0066] 1 shows the results of the marine organism adhesion test in Examples 1 to 4 and Comparative Examples 1 and 2. Marine organisms attached to the surface of the test specimen were peeled off, classified, and weighed, and the weights were added up to form a bar graph. Here, the classification of the marine organisms mentioned above was six types: barnacles, oysters (Glacian oysters, etc.), bivalves (oysters, mussels), mussels (Horsetail mussels, etc.), calcareous tubes, and bryozoans. Here, oysters in the bivalve category exclude Glacian oysters, etc., and mussels exclude Horsetail mussels, etc. Here, "Glacian oysters, etc." is meant to include what are thought to be oyster larvae.

[0067] In Figure 1, Example 1 had the least amount of marine organisms attached, and Example 2 had the second least. This is because the amount of attached copper alloy in the coating material was 900 g / m 2 This was thought to be the main reason. Also, in Example 4, although the adhesion amount of the copper alloy in the coating material was less compared to Example 3, the adhesion amount of marine organisms was less than that in Example 3. Regarding this, since Example 4 added a curing accelerator to Liquid B, the curing rate of the coating material was faster compared to Example 3. Therefore, the ratio of the copper alloy settling inside the coating material was small, and it was considered that the reason was that the copper alloy was relatively more present on the surface of the coating material. Comparative Example 1 is a specimen having only a coating material that does not contain a copper alloy on the surface, and Comparative Example 2 is a specimen of only mortar that has been surface-treated (sandblasted). Therefore, the adhesion amount of marine organisms was observed to be large compared to Examples 1 to 4, respectively.

Claims

1. An anti-fouling material for a structure that coats the surface of a structure using a coating material composed of a liquid A mainly composed of a urethane prepolymer having two or more isocyanate groups and a liquid B mainly composed of a curing agent having two or more hydroxyl groups and / or amino groups, wherein copper or copper alloy powder is adhered to the surface of the coating material.

2. The adhesion amount of the copper or copper alloy powder to the surface of the coating material is 0.1 to 5.0 kg / m ２ The anti-fouling material for marine organisms according to claim 1, which is as described above.

3. The anti-fouling material for a structure according to claim 1 or 2, wherein the copper alloy is any one of alloys composed of a copper-zinc system or a copper-tin system.

4. The anti-fouling material for a structure according to claim 1 or 2, wherein the liquid B further contains 0.1 to 15% by weight of a curing accelerator.

5. The anti-fouling material for a structure according to claim 1 or 2, wherein each of the liquid A and the liquid B does not contain a silane coupling agent or contains less than 1% by weight in at least one of them.

6. The anti-fouling material for a structure according to claim 1 or 2, wherein the structure is a concrete structure, a mortar structure, a natural stone structure, a precast structure, a metal structure, a wooden structure or a plastic structure.

7. A method for manufacturing an anti-fouling material for a structure, in which a coating material composed of a liquid A mainly composed of a urethane prepolymer having two or more isocyanate groups and a liquid B mainly composed of a curing agent having two or more hydroxyl groups and / or amino groups is spray-coated on the surface of the structure using a two-component mixing and impinging spray, and copper or copper alloy powder is adhered to the surface of the coating material after the coating and before the coating material cures.

8. The method for manufacturing an anti-fouling material for a structure according to claim 6, wherein the viscosity of each of the liquid A and the liquid B during two-component mixing and impinging is adjusted to be in the range of 500 mPa·s or less.

9. The amount of the copper or copper alloy powder adhering to the surface of the coating material is 0.1 to 5.0 kg / m ２ 8. The method for producing a marine organism adhesion prevention material according to claim 6 or 7,

10. The method for manufacturing an anti-fouling material for a structure according to claim 6 or 7, wherein the copper alloy is any one of alloys composed of a copper-zinc system or a copper-tin system.

11. The method for manufacturing an anti-fouling material for a structure according to claim 6 or 7, wherein the liquid B further contains 0.1 to 15% by weight of a curing accelerator.

12. The method for producing an anti-fouling material for marine organisms according to claim 6 or 7, wherein each of the liquid A and the liquid B does not contain a silane coupling agent or contains less than 1% by weight in at least one of them.

13. The method for producing an anti-fouling material for marine organisms according to claim 6 or 7, wherein the structure is a concrete structure, a mortar structure, a natural stone structure, a precast structure, a metal structure, a wooden structure or a plastic structure.

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