Composition for preventing adhesion of shellfish and crustaceans

Abstract

The present invention addresses the problem of providing a novel composition for preventing the adhesion of shellfish and crustaceans. The present invention provides a composition for preventing the adhesion of shellfish and crustaceans, the composition comprising at least one resin component and an iron-supplying material that is chelated with a humic acid.

Description

Composition for preventing adhesion of shellfish and crustaceans

[0001] The present invention relates to a composition for preventing the fouling of shellfish and crustaceans.

[0002] Shellfish and crustaceans such as barnacles and mussels attach to the bottom of ships, significantly reducing their functionality. For example, when these shellfish and crustaceans attach to ships and accumulate, they create irregularities on the surface of the bottom, reducing propulsion. Shellfish and crustaceans that attach to objects in this way are called marine fouling organisms, and research is being conducted to find ways to prevent their attachment. However, there is still a strong demand for the development of new methods to prevent adhesion.

[0003] JP 2007-261385 A Republished 2014 / 038596 A

[0004] The problem to be solved by the present invention is to provide a novel composition for preventing the fouling of shellfish and crustaceans.

[0005] Under these circumstances, the present inventors conducted extensive research and found that the adhesion of shellfish and crustaceans to targets can be suppressed by using a composition that combines at least one resin component and an iron supply material chelated with humic acid. The present invention is based on this novel finding. Therefore, the present invention provides the following: Item 1. A composition for preventing the adhesion of shellfish and crustaceans, comprising at least one resin component and an iron supply material chelated with humic acid.

[0006] Item 2. The composition for preventing adhesion of shellfish and crustaceans according to Item 1, wherein the resin component is at least one resin component selected from the group consisting of polyester resins, polyolefin resins, polyamide resins, alkyd resins, acrylic resins, epoxy resins, amino resins, fluororesins, silicone resins, urethane resins, vinyl resins, cellulose resins, and copolymers containing any of these.

[0007] Item 3. The composition for preventing adhesion of shellfish and crustaceans according to Item 1 or 2, wherein the humic acid is fulvic acid.

[0008] Item 4. The composition for preventing adhesion of shellfish and crustaceans according to any one of Items 1 to 3, further comprising soluble silica.

[0009] Item 5. The composition for preventing adhesion of shellfish and crustaceans according to any one of Items 1 to 4, wherein the humic acid-chelated iron supply material and / or soluble silica have a d50 (volume average particle size) in the range of 0.01 to 300 μm.

[0010] Item 6. A method for producing a composition for preventing the fouling of shellfish and crustaceans, comprising the step of mixing at least one resin component with an iron source chelated with humic acid.

[0011] Item 7. The method according to Item 6, wherein the resin component is at least one resin component selected from the group consisting of polyester resins, polyolefin resins, polyamide resins, alkyd resins, acrylic resins, epoxy resins, amino resins, fluororesins, silicone resins, urethane resins, vinyl resins, cellulose resins, and copolymers containing any of these.

[0012] Item 8. The method according to Item 6 or 7, wherein the humic acid chelated iron supply material is a fulvic acid iron silica material.

[0013] Item 9. The method according to any one of Items 6 to 8, wherein the fulvic acid iron silica material is a soluble silica-containing fulvic acid iron produced by mixing 50 mg to 7000 mg of polysilica iron liquid (PSI) with 1 kg of a fermented product produced by fermenting and sterilizing sewage sludge and wood chips to produce fulvic acid, and then aging the mixture.

[0014] Item 10. A coating composition for preventing adhesion of shellfish and crustaceans, comprising the composition according to any one of items 1 to 5.

[0015] Item 11. A film for preventing adhesion of shellfish and crustaceans, comprising the composition according to any one of items 1 to 5.

[0016] Item 12. A resin molded article for preventing adhesion of shellfish and crustaceans, comprising the composition according to any one of items 1 to 5.

[0017] Item 13. A method for preventing the attachment of shellfish and crustaceans to a substrate, comprising the steps of: applying the composition according to any one of Items 1 to 5 to a substrate; and drying the applied composition to form a film.

[0018] According to the present invention, a novel composition for preventing the adhesion of shellfish and crustaceans can be provided. Furthermore, the composition of the present invention can be applied to objects of various shapes to form a film, and the composition itself can also be used to produce resin molded articles of various shapes. Therefore, according to the present invention, treatment to prevent the adhesion of shellfish and crustaceans can be performed on a variety of locations.

[0019] The present invention provides a composition for preventing the fouling of shellfish and crustaceans, comprising at least one resin component and an iron source chelated with humic acid.

[0020] The shellfish and crustaceans that are the targets of adhesion prevention by the present invention are not particularly limited, but examples of shellfish include the genus Mytilus (Mytilus edulis, Mytilus galli, Mytilus edulis, Mytilus mussel, Mytilus edulis, Mytilus mussel, etc.), the genus Limnoperna (Limnoperna maritima, Limnoperna maritima, Limnoperna maritima, etc.), the genus Limnoperna (Illicola stenophylla, etc.), the genus Limnoperna maritima (Limnoperna maritima, Limnoperna maritima ... oysters, etc. Furthermore, examples of crustaceans include barnacles, etc.

[0021] Examples of the resin component include polyester resins, polyolefin resins, polyamide resins, alkyd resins, acrylic resins, epoxy resins, amino resins, fluororesins, silicone resins, urethane resins, vinyl resins, cellulose resins, and copolymers containing these. These resins may be used alone or in combination of two or more.

[0022] As the polyester resin, a wide variety of polymers having an ester bond can be used, for example, polyester polyols, etc. Examples of polyester polyols include those obtained by polycondensation of a low-molecular-weight diol and a dibasic acid, and those obtained by ring-opening reaction of a lactone compound using a low-molecular-weight diol as an initiator.

[0023] In the former case, examples of the low molecular weight diol include ethylene glycol, propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, alkane (C7 to C22) diol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, cyclohexanedimethanol, alkane-1,2-diol (C17 to C20), hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bishydroxyethoxybenzene, xylene glycol, and bis-2-hydroxyethylene terephthalate.

[0024] Examples of dibasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, etc. The low molecular weight diols and dibasic acids may be used either alone or in combination of two or more.

[0025] In the latter case, examples of the lactone compound include ε-caprolactone and polyβ-methyl-δ-valerolactone.

[0026] Examples of alkyd resins include resins obtained by esterifying drying oil fatty acids and / or semi-drying oil fatty acids, acid components other than the drying oil fatty acids and / or semi-drying oil fatty acids, and alcohol components by known methods. Although drying oil fatty acids and semi-drying oil fatty acids cannot be strictly distinguished from each other, drying oil fatty acids are usually unsaturated fatty acids with an iodine value of 130 or more, and semi-drying oil fatty acids are usually unsaturated fatty acids with an iodine value of 100 or more but less than 130. On the other hand, non-drying oil fatty acids are usually fatty acids with an iodine value of less than 100.

[0027] Examples of drying oil fatty acids and semi-drying oil fatty acids include unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, eleostearic acid, and ricinoleic acid, fish oil fatty acids, dehydrated castor oil fatty acids, safflower oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, sesame oil fatty acids, poppy seed oil fatty acids, perilla oil fatty acids, hemp seed oil fatty acids, grape kernel oil fatty acids, corn oil fatty acids, tall oil fatty acids, sunflower oil fatty acids, cottonseed oil fatty acids, walnut oil fatty acids, rubber seed oil fatty acids, hygienic acid fatty acids, and combinations thereof.

[0028] Examples of the acid component include benzoic acid, p-tert-butylbenzoic acid, phthalic acid (anhydride), hexahydrophthalic acid (anhydride), tetrahydrophthalic acid (anhydride), tetrachlorophthalic acid (anhydride), hexachlorophthalic acid (anhydride), tetrabromophthalic acid (anhydride), trimellitic acid, "Himic Acid" (a product of Hitachi Chemical Co., Ltd.; "Himic Acid" is a registered trademark of the company), succinic acid (anhydride), maleic acid (anhydride), fumaric acid, itaconic acid (anhydride), adipic acid, sebacic acid, oxalic acid, and combinations thereof.

[0029] In addition, as the acid component, saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, etc., and non-drying oil fatty acids such as hydrogenated coconut oil fatty acid, coconut oil fatty acid, palm oil fatty acid, etc. These acid components can be used alone or in combination of two or more.

[0030] Examples of the alcohol component include ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, neopentyl glycol, 1,6-hexanediol, 1,6-hexanetriol, pentaerythritol, sorbitol, and combinations thereof. These alcohol components can be used alone or in combination of two or more.

[0031] The alkyd resin may be an acrylic-modified alkyd resin, a urethane-modified alkyd resin, a phenol-modified alkyd resin, a fatty acid-modified acrylic resin, or the like.

[0032] Examples of polyolefin resins include radical homopolymers or copolymers of at least one olefin selected from ethylene, propylene, butene, methylbutene, isoprene, etc., and radical copolymers of such olefins with vinyl acetate, butadiene, acrylic acid esters, methacrylic acid esters, etc.

[0033] Examples of acrylic resins include resins obtained by copolymerizing a polymerizable unsaturated monomer component containing a (meth)acryloyl compound as an essential component and other polymerizable unsaturated monomers.

[0034] Examples of the (meth)acryloyl compound include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and "isostearyl acrylate" (manufactured by Osaka Organic Chemical Industry Co., Ltd., ISTA linear or branched alkyl (meth)acrylates such as highly branched long-chain alkyl acrylates; alicyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate and 2-ethoxyethyl (meth)acrylate; fluoroalkyl (meth)acrylates such as hexafluoroisopropyl (meth)acrylate, perfluorooctylmethyl (meth)acrylate, and perfluorooctylethyl (meth)acrylate; (2-(meth)acryloyloxyethyl) acid phosphate, (2-(meth)acryloyloxyethyl) ) acryloyloxypropyl) acid phosphate and other phosphate group-containing (meth)acrylates; N,N-dialkylaminoalkyl (meth)acrylates such as N,N-diethylaminoethyl (meth)acrylate; (meth)acrylamide; (meth)acrylic acid; carbonyl group-containing (meth)acryloyl monomers such as acetoacetoxyethyl (meth)acrylate and diacetone (meth)acrylamide; epoxy group-containing (meth)acryloyl monomers such as glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate and 3,4-epoxycyclohexylpropyl (meth)acrylate; isocyanato group-containing (meth)acryloyl monomers such as isocyanatoethyl (meth)acrylate;Alkoxysilyl group-containing (meth)acryloyl monomers such as γ-(meth)acryloyloxypropyltrimethoxysilane and γ-(meth)acryloyloxypropyltriethoxysilane; Polyvinyl compounds such as allyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, 1,1,1-trishydroxymethylethane di(meth)acrylate, 1,1,1-trishydroxymethylethane tri(meth)acrylate, and 1,1,1-trishydroxymethylpropane tri(meth)acrylate; Oxidatively curable group-containing (meth)acryloyl monomers such as dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyloxypropyl (meth)acrylate, and dicyclopentenyl (meth)acrylate; 1,2,2,6,6-pentamethylpiperidyl (meth)acrylate, 2,2,6,6-tetramethylpiperidinyl (meth)acrylate, and the like; 2-((meth)acryloyloxy)ethyltrimethylammonium chloride, 2-((meth)acryloyloxy)ethyltrimethylammonium bromide, and (meth)acryloylaminopropyltrimethylammonium quaternary ammonium salt group-containing (meth)acrylates such as ammonium chloride, (meth)acryloylaminopropyltrimethylammonium bromide, tetrabutylammonium (meth)acrylate, tetramethylammonium (meth)acrylate, trimethylbenzylammonium (meth)acrylate, and 2-((meth)acryloyloxy)ethyltrimethylammonium dimethylphosphate; and (meth)acrylates having a polyoxyalkylene chain whose molecular terminal is an alkoxy group, which can be used either alone or in combination of two or more types.

[0035] Other polymerizable unsaturated monomers include, for example, (meth)acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl aromatic compounds such as styrene and α-methylstyrene; carboxyl group-containing polymerizable unsaturated monomers such as maleic acid, crotonic acid, and β-carboxyethyl acrylate; carbonyl group-containing polymerizable unsaturated monomers such as (meth)acrolein, formylstyrene, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), and acetoacetoxy allyl ester; and epoxy group-containing polymerizable unsaturated monomers such as allyl glycidyl ether. isocyanato group-containing polymerizable unsaturated monomers such as m-isopropenyl-α,α-dimethylbenzyl isocyanate; alkoxysilyl group-containing polymerizable unsaturated monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; oxidatively curable group-containing polymerizable unsaturated monomers such as reaction products of epoxy group-containing polymerizable unsaturated monomers or hydroxyl group-containing polymerizable unsaturated monomers with unsaturated fatty acids; and fluorovinyl ethers such as fluoroalkyltrifluorovinyl ether and perfluoroalkyltrifluorovinyl ether, and the like. These may be used alone or in combination of two or more.

[0036] The at least one resin component may also include a chlorinated resin. Examples of chlorinated resins include vinyl chloride resins, chlorinated rubber resins, chlorinated polyethylene resins, chlorinated polypropylene resins, vinyl chloride-vinyl isobutyl ether copolymers, and vinyl chloride-vinyl acetate copolymers, with chlorinated copolymer resins being preferred. Examples of chlorinated copolymer resins include vinyl chloride-vinyl acetate copolymers. In the present invention, "vinyl chloride-vinyl acetate copolymers" include not only copolymers of vinyl chloride and vinyl acetate (vinyl chloride-vinyl acetate copolymers), but also copolymers containing monomers other than vinyl chloride and vinyl acetate as raw materials (e.g., vinyl chloride-vinyl acetate-maleic acid copolymers, vinyl chloride-vinyl acetate-(meth)acrylic acid-(meth)acrylic acid ester copolymers, etc.). These chlorinated resins may be used alone or in combination of two or more.

[0037] As used herein, "(meth)acrylate" refers to acrylate and / or methacrylate, "(meth)acrylic acid" refers to acrylic acid and / or methacrylic acid, "(meth)acryloyl" refers to acryloyl and / or methacryloyl, and "(meth)acrylamide" refers to acrylamide and / or methacrylamide.

[0038] There are no restrictions on the weight average molecular weight of these resins, but from the viewpoint of film-forming properties and coating strength, the range is, for example, 10,000 to 300,000, preferably 30,000 to 200,000, and more preferably 50,000 to 100,000.

[0039] Humic Acid Chelated Iron Supply Material In the present invention, the humic acid chelated iron supply material can be prepared by mixing humic acid with an iron supply material.

[0040] Examples of humic acids include fulvic acid and humic acid, with fulvic acid being preferred. In this specification, fulvic acid refers to a component of humic substances that dissolves in alkali and acid. The molecular weight of fulvic acid is not limited, but examples include those with a weight-average molecular weight of less than 10,000 (e.g., 7,000 or less, 5,000 or less, 3,000 or less, etc.). In this specification, humic acid refers to a component of humic substances that dissolves in alkali and in acid. The molecular weight of humic acid is not limited, but examples include those with a weight-average molecular weight of 10,000 or more but less than 100,000 (e.g., 70,000 or less, 50,000 or less, 30,000 or less, etc.). Here, humic substances refer to products obtained by microbial decomposition of dead plants, animal carcasses, etc. in soil. Humic substances typically contain various organic compounds. These humic acids can be used alone or in combination.

[0041] Examples of iron supplying materials include polysilica iron liquid (PSI), metal particles such as steel slag, iron powder, iron oxide, etc., and polysilica iron liquid (PSI) is preferred. These iron supplying materials can be used alone or in combination of two or more.

[0042] The mixing ratio of the iron supply material and humic acid is not limited, but it is preferable to mix the iron supply material and humic acid so that the humic acid content is 30 to 90 parts by mass, preferably 45 to 75 parts by mass, per part by mass of the iron component contained in the iron supply material. In this specification, the content of the "iron component" means the total content of iron ions released from iron and iron compounds (iron oxide, etc.) contained in the iron supply material.

[0043] In preparing the humic acid-chelated iron supply material, it is preferable to mix the humic acid with the iron supply material and then age the mixture. In the present invention, examples of the humic acid-chelated iron supply material include iron-silica fulvic acid materials, iron-fulvic acid materials, humic acid-silica materials, and humic acid-iron materials, with iron-fulvic acid-silica materials being preferred.

[0044] In the present invention, the d50 (volume average particle size) of the humic acid-chelated iron supply material is not limited and may be, for example, 0.01 to 300 μm, preferably 0.1 to 200 μm, and more preferably 1 to 50 μm. From the viewpoints of crack resistance and water-resistant adhesion, the above range is preferable. The d50 (volume average particle size) refers to the median diameter, and more specifically, the particle size at which the cumulative particle size distribution from the small particle size side in the volume-based particle size distribution is 50%. In the present invention, the d50 (volume average particle size) can be measured by measuring the volume-based particle size distribution by laser diffraction scattering using a submicron particle size distribution analyzer "Microtrac MT3000" (trade name, manufactured by Microtrac Bell).

[0045] The following description will be given taking a fulvic acid iron-silica material as a non-limiting preferred example of an iron-supply material chelated with humic acid, but the present invention is not limited to such an embodiment.

[0046] In the present invention, the iron-silica fulvic acid material can be produced by, for example, mixing 50 mg to 7000 mg of polysilica iron liquid (PSI) with 1 kg of a fermented product produced by fermenting and sterilizing sewage sludge and wood chips to produce fulvic acid, and then aging the mixture. The iron-silica fulvic acid can be produced in accordance with the method described in Patent Document 2. Specifically, for example, the method is as follows.

[0047] In the present invention, the target to which the polysilica iron liquid agent (PSI) is added can be a fermented product obtained by fermenting and sterilizing sewage sludge and wood chips. For example, in the fermentation step for preparing the fermented product, harmful microorganisms can be killed or inactivated by adjusting the fermentation temperature and time.

[0048] As the polysilica iron liquid agent (PSI), commercially available products can be used as appropriate. The use of a polysilica iron liquid agent (PSI) containing iron and silica as its main components is preferred because it supplies soluble silica and iron, allowing soluble silica and fulvic acid iron to be easily eluted into water and soil.

[0049] The amount of polysilica iron liquid (PSI) added to the fermentation treatment product is 50 mg / kg to 7000 mg / kg, preferably 500 mg / kg to 5000 mg / kg, per mass (kg) of the fermentation treatment product. From the viewpoint of inhibiting adhesion of marine fouling organisms, the above range is preferable. In addition, the amount of silica iron (FeCl ) contained in the polysilica iron liquid (PSI) is ３ +Na ２ O.nSiO ２ ・xH ２ In O), it is preferable to add PSI so that the amount of PSI per mass (kg) of the fermentation product is preferably 3.5 mg / kg to 2030 mg of silicate iron / kg of fermentation product, more preferably 7 mg / kg to 1450 mg of silicate iron / kg of fermentation product.

[0050] In the present invention, the d50 (volume average particle size) of the iron silica fulvate material is not limited, and is, for example, 0.01 to 300 μm, preferably 0.1 to 200 μm, and more preferably 1 to 50 μm. From the viewpoints of crack resistance and water-resistant adhesion, the above range is preferable.

[0051] The ratio of the iron component to the silica content in the iron fulvic acid silica material is not limited, and may be, for example, 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, of the latter per 1 part by mass of the former. In this specification, the content of the "iron component" refers to the total content of iron contained in the iron fulvic acid silica material and iron ions released from iron compounds (iron oxide, etc.). The ratio of the iron component to the fulvic acid content in the iron fulvic acid silica material is also not limited, and may be, for example, 30 to 90 parts by mass, preferably 45 to 75 parts by mass, of the latter per 1 part by mass of the former.

[0052] The adhesion prevention composition of the present invention preferably further contains soluble silica. In this embodiment, the soluble silica may be blended into the composition separately from at least one resin component and the humic acid-chelated iron supply material, or the composition may be prepared using a material containing soluble silica as the iron supply material (e.g., a fulvic acid iron-silica material). When soluble silica is used, its content is not limited, and the ratio of the iron component derived from the iron supply material to silica is, for example, 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, per 1 part by mass of the former.

[0053] The composition of the present invention can be obtained, for example, by a method comprising the step of mixing the at least one resin component (unless otherwise specified, the resin component described in the section "At least one resin component" above will hereinafter simply be referred to as the resin component) with the humic acid-chelated iron supply material (e.g., a fulvic acid iron-silica material). Thus, in one embodiment, the present invention provides a method for producing a composition for preventing the fouling of shellfish and crustaceans, comprising the step of mixing at least one resin component with a humic acid-chelated iron supply material.

[0054] In the present invention, the blending ratio of the resin component to the humic acid-chelated iron supply material is not limited, but for example, the latter can be used in a range of 0.01 to 10 parts by mass, preferably 0.1 to 8 parts by mass, and more preferably 1 to 6 parts by mass, per 1 part by mass of the former. From the viewpoint of crack resistance, it is preferable that the blending ratio of the resin component to the humic acid-chelated iron supply material be in the above range.

[0055] The resin component and the humic acid-chelated iron supply material can be mixed using a method known per se. For example, a disperser, shaker, bead mill, ball mill, pebble ball mill, homogenizer, ultrasonic disperser, kneader, extruder, planetary kneader, etc. can be used. The temperature during mixing is not particularly limited and can be set, for example, in the range of 0 to 60°C, preferably 20 to 40°C. The mixing time is also not limited and can be set, for example, in the range of 0.05 to 5 hours, preferably 0.1 to 2 hours.

[0056] In the step of mixing the resin component and the humic acid-chelated iron supply material in the present invention, the resin component may be used in a state mixed with other raw materials. The humic acid-chelated iron supply material may also be used in a state mixed with other raw materials. Therefore, in the present invention, the "step of mixing at least one resin component and a humic acid-chelated iron supply material" is not limited as long as the resin component and the humic acid-chelated iron supply material are mixed. It may include mixing only the resin component and only the humic acid-chelated iron supply material; mixing a mixture containing the resin component and other raw materials with the humic acid-chelated iron supply material; mixing the resin component with a mixture containing the humic acid-chelated iron supply material and other raw materials; or mixing a mixture containing the resin component and other raw materials with a mixture containing the humic acid-chelated iron supply material and other raw materials.

[0057] Examples of raw materials other than the resin component and the humic acid-chelated iron supply material include plasticizers. Examples of plasticizers include phosphate esters (e.g., tricresyl phosphate), chlorinated paraffins (e.g., chlorinated normal paraffin), liquid paraffin, n-paraffin, phthalate esters (e.g., isodecyl phthalate), polyester resins (e.g., Polycizer P-29, manufactured by Dainippon Ink & Chemicals, Inc.), epoxidized oils (e.g., Epoxidized Soybean Oil, Adeka Cizer O-130P, manufactured by Adeka Argus Chemical Co., Ltd.), polybutene, terpene phenols, and polyvinyl ethyl ether. These plasticizers can be used alone or in combination of two or more. When a plasticizer is used, the amount used is not limited; for example, 0.001 to 1 part by mass, preferably 0.01 to 0.5 parts by mass, of the plasticizer can be used per 1 part by mass of the resin component.

[0058] In addition, thickeners may be used as raw materials other than the resin component and the humic acid-chelated iron supply material. Examples of thickeners include organic thickeners such as oxidized polyethylene wax, polyethylene wax, fatty acid amide wax, castor oil wax, and dimer acid esters; and inorganic thickeners such as micronized silica, bentonite, silica surface-treated with a silane compound, bentonite surface-treated with a quaternary ammonium salt (organic bentonite), and surface-treated calcium carbonate. These thickeners can be used alone or in combination. Commercially available thickeners, such as DISPARLON NS-30 (containing polyethylene oxide and fatty acid amide wax), can also be used. When a thickener is used, the amount used is not limited; for example, 0.001 to 0.5 parts by mass, preferably 0.01 to 0.3 parts by mass, of the thickener component can be used per 1 part by mass of the resin component.

[0059] A solvent may also be used as a raw material other than the resin component and the humic acid-chelated iron supply material. Examples of solvents include hydrocarbon solvents such as n-butane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, and cyclobutane; aromatic solvents such as toluene, xylene, and ethylbenzene; ether solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and diethylene glycol; ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, and butyl carbitol acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; and alcohol solvents such as ethanol, isopropanol, n-butanol, sec-butanol, and isobutanol. These solvents may be used alone or in combination. When a solvent is used, the amount used is not limited, but for example, the solvent can be used in an amount of 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass, per part by mass of the resin component.

[0060] Other raw materials than the resin component and the humic acid-chelated iron supply material may include, for example, nutrient components. Examples of the nutrient components include nitrogen-containing substances, phosphorus-containing substances, alkali metal-containing substances, and alkaline earth metal-containing substances, which are generally known as fertilizers for cultivated plants and are effective as nutrients for seaweed. These substances may also include substances containing two or more of the above atoms, such as lime nitrogen, bone meal, and scale meal, which contain nitrogen, calcium, and trace amounts of other atoms (e.g., phosphorus) in combination. More specifically, the following may be mentioned: Nitrogen-containing substances (ammonium sulfate, urea, lime nitrogen, ammonium chloride, ammonium nitrate, ammonium phosphate, metal salts of ethylenediaminetetraacetic acid (EDTA), defatted soybean flour, chicken manure, cow manure, amino acid salts, guanylurea salts, guanidine salts, oil cake, glycine, chemical fertilizers, etc.), phosphorus-containing substances (calcium superphosphate, calcium triphosphate, calcium metaphosphate, ammoniacal calcium triphosphate, soluble phosphate fertilizer, condensed phosphates, etc.), alkali metal-containing substances (potassium chloride, potassium phosphate, potassium sulfate, potassium nitrate, seaweed ash, wood ash, etc.), alkaline earth metal-containing substances (oyster shell organic lime, bone meal, fish meal, scale shell, crab shell, calcium carbonate, etc.), etc. Nutrients containing multiple atoms are listed as a representative in the names of substances containing a single atom for convenience. The above-listed substances are only a portion of the nutrient components that can be used in the present invention. Fertilizer substances or nutrient components containing the above atoms alone or in combination can also be used without particular limitations. These nutrient components can be used alone or in combination of two or more. Among these substances, one, preferably two or more, nutrient components selected from nitrogen-containing substances and alkaline earth metal-containing substances are preferably used. When two or more nutrient components are used in combination, there are no strict limitations on the ratio of their use. When nutrient components are used, their amount is not limited; for example, 0.1 to 5 parts by mass, preferably 0.3 to 3 parts by mass, of the nutrient components can be used per 1 part by mass of the resin component. Applying the composition of the present invention to an article to which a material for promoting algae growth has been added can prevent shellfish and crustaceans from attaching to the article, contributing to the efficient growth of blue carbon.In particular, in such an embodiment, it is preferable to incorporate nutritional ingredients.

[0061] Furthermore, in addition to the above substances, the composition for preventing adhesion of shellfish and crustaceans may also contain known additives, curing accelerators, antifouling agents, color pigments, etc. that are commonly used in paints for the purpose of adjusting the paint viscosity, storage stability, paint workability, color tone, antifouling properties, and the state and physical properties of the paint film.

[0062] As described above, in the method of the present invention, the resin component is preferably at least one selected from the group consisting of polyester resin, polyolefin resin, polyamide resin, alkyd resin, acrylic resin, epoxy resin, amino resin, fluororesin, silicone resin, urethane resin, vinyl resin, cellulose resin, and copolymers containing these. Furthermore, a fulvic acid iron silica material is preferred as the humic acid-chelated iron supply material. As also described above, in a preferred embodiment, the fulvic acid iron silica material may be fulvic acid iron containing soluble silica, which is produced by mixing 50 mg to 7000 mg of polysilica iron (PSI) with 1 kg of fermented product produced by fermenting and sterilizing sewage sludge and wood chips to produce fulvic acid, followed by aging. Therefore, in a preferred embodiment, the present invention provides a method for producing a composition for preventing the adhesion of shellfish and crustaceans, comprising the step of mixing at least one resin component with a fulvic acid iron silica material, wherein the resin component is at least one resin component selected from the group consisting of polyester resins, polyolefin resins, polyamide resins, alkyd resins, acrylic resins, epoxy resins, amino resins, fluororesins, silicone resins, urethane resins, vinyl resins, cellulose resins, and copolymers containing any of these, and the fulvic acid iron silica material is soluble silica-containing fulvic acid iron produced by mixing 50 mg to 7000 mg of polysilica iron liquid (PSI) with 1 kg of a fermented product produced by fermenting and sterilizing sewage sludge and wood chips to produce fulvic acid, and then aging the mixture.

[0063] The composition obtained by the above method can be used, for example, by applying it to a substrate and drying it to form a coating film. Therefore, the composition of the present invention can be used as a coating composition. The material of the substrate is not limited, and examples include resins (vinyl chloride, polyester, acrylic, FRP, etc.), metals (steel, aluminum, stainless steel, etc.), concrete, rock, wood, fibers, biodegradable fibers, and resin-coated metals. Resins, resin-coated metals, and concrete are preferred. The shape of the substrate is also not limited, and examples include plate-like, string-like, net-like, mesh-like, and combinations thereof. The method of applying the coating composition to the substrate is not limited, and examples include applicators, bar coaters, sprayers, immersing, rollers, brushes, and flow coating. The thickness of the coating film is not limited, and can be set to a dry film thickness of, for example, 50 to 3,000 μm, preferably 100 to 1,000 μm. Examples of substrates include ship bottoms, fishing nets, fishing gear, buoys, seawater desalination facilities, water intake pits for thermal power plants, seawater cooling facilities for power plants, etc., and scaffolding for growing algae. Accordingly, in one embodiment, the present invention provides a film for preventing adhesion of shellfish and crustaceans, comprising the composition of the present invention. In this embodiment, examples of the film of the present invention include a composition comprising the at least one resin component and an iron source chelated with humic acid, in a dried and / or hardened state.

[0064] In one embodiment, a resin molded article in which adhesion of shellfish and crustaceans is suppressed can be obtained by producing the resin molded article using the composition of the present invention itself. Thus, the present invention provides a resin molded article for preventing adhesion of shellfish and crustaceans, which contains the composition of the present invention. The resin molded article can be produced using a known molding method (injection molding, compression molding, extrusion molding, blow molding, foam molding, etc.) other than using the composition of the present invention.

[0065] The present invention will be described in more detail below with reference to examples, but is not limited to these examples.

[0066] Comparative Example 1: Vinyl chloride / vinyl acetate copolymer resin "SOLBIN AL" (vinyl chloride / vinyl acetate / vinyl alcohol = 92.5 / 2.5 / 5, polymerization degree 300, molecular weight Mw = 5.3x10) manufactured by Nissin Chemical Industry Co., Ltd. ４ The coating composition of Comparative Example 1 was prepared by dissolving 113 g of acrylic acid (hydroxyl value 64 mg KOH / g) and 17 g of Adeka Cizer O-130P manufactured by ADEKA CORPORATION in 230 g of methyl isobutyl ketone and 230 g of "mixed xylene" (xylene / ethylbenzene mixed liquid) manufactured by Maruzen Petrochemical Co., Ltd., and mixing and dispersing the solution at a stirring speed of about 2,000 rpm using a disper.

[0067] The resulting coating composition was applied to a transparent polyvinyl chloride plate measuring 200 mm wide, 300 mm long and 2.0 mm thick using a bar coater so that the dry film thickness was 300 μm. The plate was then left at room temperature for at least 3 days to dry out the solvent and form a coating film, thereby producing a test plate for marine evaluation.

[0068] Example 1: Vinyl chloride / vinyl acetate copolymer resin "SOLBIN AL" (vinyl chloride / vinyl acetate / vinyl alcohol = 92.5 / 2.5 / 5, polymerization degree 300, molecular weight Mw = 5.3 × 10) manufactured by Nissin Chemical Industry Co., Ltd. ４113 g of ammonium nitrate (hydroxyl value 64 mg KOH / g) and 17 g of ADEKA Cizer O-130P manufactured by ADEKA Corporation were dissolved in 230 g of methyl isobutyl ketone and 230 g of "mixed xylene" (xylene / ethylbenzene mixture) manufactured by Maruzen Petrochemical Co., Ltd., and 402 g of iron supply material 1 shown below was mixed and dispersed into the solution using a disperser at a stirring speed of approximately 2,000 rpm to prepare the coating composition of Example 1. Except for using the coating composition obtained above, a coating film was formed on a hard PVC plate in the same manner as in Comparative Example 1, to prepare a test plate for marine evaluation. (Iron Supply Material 1) "Granular Fulvic Iron," a fulvic acid iron material manufactured by PIC Bio Co., Ltd., was prepared by the following method. After coarsely pulverizing in a 10L Henschel mixer at 2000 rpm for 10 seconds, the material was finely pulverized using an FA-SW-1 atomizer with a main rotor inverter frequency set to 45 Hz (= 1350 rpm) for one pass. The pulverized material was sieved using a vibrating sieve with a 150 mesh opening. The particle size distribution of iron feed material 1 was measured using a laser diffraction / scattering particle size distribution analyzer.

[0069] Examples 2-3 and Comparative Example 2 Examples 2-3 and Comparative Example 2 were obtained in the same manner as Example 1, except that the formulations shown in Table 1 were used. Iron supply material 2 (D50 20 μm) and iron supply material 3 were prepared as follows. Furthermore, a coating film was formed on a hard PVC plate in the same manner as Comparative Example 1, except that the coating composition obtained above was used, to prepare a test plate for marine evaluation. (Iron supply material 2 (D50 20 μm)) Iron supply material 2 (D50 20 μm) was obtained in the same manner as iron supply material 1, except that the iron fulvic acid silica material "Ryugu no Tsukai" manufactured by Koyo Co., Ltd. was used instead of the iron fulvic acid material "Granular Fulvic Iron" manufactured by PIC Bio Co., Ltd. "Ryugu no Tsukai" was produced by spraying and mixing 5 kg of a silica iron-based liquid substance (PSI-025 manufactured by Taiki Pharmaceutical Co., Ltd.) with 10 tons of fermented sewage sludge and wood chip mixture, and then aging the mixture in a warehouse for 20 days. The composition of the silica iron liquid material (PSI-025) is as follows: Iron (III) chloride (FeCl ３ ) 5-27 wt / wt% Sodium silicate (Na ２ O.nSiO ２ ・xH ２O (n=approx. 3) 2wt / wt% (SiO ２ (as) sulfuric acid 1 wt / wt% water 70-92 wt / wt%.

[0070] The analytical values ​​of the active ingredients in the obtained "Ryugu no Tsukai" are as follows: Fulvic acid 2,400 mg / L Soluble iron 39 mg / L Soluble silica 105 mg / L The above analytical values ​​were obtained by storing 50 g of "Ryugu no Tsukai" in 100 ml of deionized water at room temperature for 20 days, and then filtering the filtrate through 5A filter paper. Fulvic acid and soluble iron were analyzed by Japan Food Functional Analysis Research Institute, Inc. Soluble silica was analyzed using an ICP-MS analyzer at Kurume Research Park, Inc.

[0071] The obtained "Dragon Palace Messenger" was coarsely pulverized in a 10-liter Henschel mixer at 2000 rpm for 10 seconds, and then finely pulverized using an FA-SW-1 atomizer with a main rotor inverter frequency set to 45 Hz (1350 rpm) for one pass. The pulverized material was sieved through a 150-mesh sieve in a vibrating sieve to obtain Iron Supply Material 2 (D50 20 μm). The particle size distribution of the obtained Iron Supply Material 2 (D50 20 μm) was measured using a laser diffraction / scattering particle size distribution analyzer. (Iron Supply Material 3) Iron Supply Material 3 was obtained in the same manner as Iron Supply Material 1, except that "Chelate Marine K1 Type," a fulvic acid iron silica material manufactured by Hinomaru Sangyo Co., Ltd., was used instead of "Granular Fulvic Iron," a fulvic acid iron material manufactured by PIC Bio Corporation. In the above table, examples and comparative examples with "-" in the "Substrate" column indicate that a resin molded article was produced using the respective composition.

[0072] Example 4: 113 g of PARALOID B-44 Resin (100% solids) acrylic resin manufactured by DOW Corp. and 17 g of Adeka Cizer O-130P manufactured by ADEKA Corp. were dissolved in 230 g of methyl isobutyl ketone and 230 g of "mixed xylene" (xylene / ethylbenzene mixture) manufactured by Maruzen Petrochemical Co., Ltd., and 402 g of iron supply material 2 (D50 20 μm) shown below was mixed and dispersed into the solution using a disperser at a stirring speed of approximately 2,000 rpm to prepare the coating composition of Example 4. A coating film was formed on a rigid PVC plate in the same manner as in Comparative Example 1, except that the coating composition obtained above was used, and a test plate for marine evaluation was prepared.

[0073] Example 5: 141 g of polyester polyol resin XR-1016 (solids content 80%, hydroxyl value 70 mg KOH / g) manufactured by Toshin Yushi Co., Ltd. and 17 g of Adeka Cizer O-130P manufactured by ADEKA Corporation were dissolved in 216 g of methyl isobutyl ketone and 216 g of "mixed xylene" (xylene / ethylbenzene mixture) manufactured by Maruzen Petrochemical Co., Ltd., and 402 g of iron supply material 2 (D50 20 μm) shown below was mixed and dispersed into the solution using a disperser at a stirring speed of approximately 2,000 rpm to prepare the coating composition of Example 5. A coating film was formed on a rigid PVC plate in the same manner as in Comparative Example 1, except that the coating composition obtained above was used, and a test plate for marine evaluation was prepared.

[0074] Example 6 A coating composition of Example 6 was obtained in the same manner as in Example 1, except that the formulation was as shown in Table 1. A coating film was formed on a hard PVC plate in the same manner as in Comparative Example 1, except that the coating composition obtained above was used, to prepare a test plate for marine evaluation.

[0075] Example 7 A coating composition was obtained in the same manner as in Example 1, except that the composition was as shown in Table 1. A polyethylene terephthalate net was prepared as a substrate. The net was immersed in the obtained coating composition, and then removed from the coating. The excess coating was removed, and the net was air-dried and then fixed to a 35 cm x 45 cm iron frame.

[0076] Example 8: 70 g of polypropylene resin with an MFR (temperature 230°C, load 2.16 kg) of 45 g / 10 min was mixed with 30 g of iron supply material 2 (D50 20 μm). The resulting mixture was melt-kneaded using a twin-screw kneading extruder, and the melt-kneaded product was extruded into a strand shape and then cut to prepare resin pellets. The resin pellets were injection-molded using an injection molding machine to produce a sheet measuring 300 mm in length, 200 mm in width, and 1 mm in thickness, which was used as a test plate for marine evaluation in the present example.

[0077] Example 9: The coating composition of Example 9 was obtained in the same manner as in Example 1, except for the formulation shown in Table 1. Iron supply material 2 (D50 150 μm) was prepared as follows. A coating film was formed on a hard PVC plate in the same manner as in Comparative Example 1, except for using the coating composition obtained above, to prepare a test plate for marine evaluation. (Iron supply material 2 (D50 150 μm)) Iron supply material 2 (D50 150 μm) was obtained in the same manner as Iron supply material 2 (D50 20 μm), except for the inverter frequency setting and mesh sieve openings as shown below. The "Dragon Palace Messenger" was coarsely pulverized in a 10-liter Henschel mixer at 2000 rpm for 10 seconds, and then finely pulverized in an FA-SW-1 atomizer with a main rotor inverter frequency setting of 35 Hz (=1050 rpm) for one pass. The pulverized product was sieved using a 50-mesh sieve in a vibrating sieve to obtain iron supply material 2 (D50 150 μm). The particle size distribution of the obtained iron supply material 2 (D50 150 μm) was measured using a laser diffraction / scattering particle size distribution measuring device.

[0078] Example 10 A coating composition of Example 10 was obtained in the same manner as in Example 1, except for using the formulation shown in Table 1. The obtained coating composition was applied to a concrete block 20 cm wide, 10 cm deep, and 6 cm high with a bar coater so as to give a dry film thickness of 300 μm, and the block was left to stand at room temperature for 3 days or more to dry the solvent and form a coating film, thereby producing a test panel for marine evaluation.

[0079] Examples 11 to 13 The coating compositions of Examples 11 to 13 were obtained in the same manner as in Example 1, except for using the formulations shown in Table 1. Except for using the coating compositions obtained above, a coating film was formed on a hard PVC plate in the same manner as in Comparative Example 1, to prepare a test plate for marine evaluation.

[0080] Comparative Example 3 A sheet was produced in the same manner as in Example 8 above using only resin not containing iron supply materials 1 to 3, specifically the composition shown in Table 1, to prepare a comparative marine evaluation test plate.

[0081] Marine Evaluation Test: The marine evaluation test panels prepared in this manner were fixed to a tidal flat 100 meters offshore in the Ariake Sea in Nagasu Town, Tamana District, Kumamoto Prefecture, using stakes. The test site has an average tide level of approximately 3-4 m and a maximum tide level of 5-6 m. Three months after installation, crack resistance and antifouling performance tests were conducted. Crack Resistance Test: The coating on the test specimen was visually inspected for cracks. S: No cracks were observed; A: Fine cracks were observed on a portion of the coating surface; B: Fine or clear cracks were observed over a wide area of ​​the coating surface; C: Cracks extending to the substrate were observed. A grade of B or higher is considered acceptable, with A being preferred over B, and S being the most preferable. Antifouling Performance Test: A: After submersion in the sea, the area of ​​the coating surface covered by attached aquatic organisms such as shellfish and crustaceans was less than 30% of the surface area before submersion in seawater. B: On the coating surface after being placed in the sea, the area on which three attached aquatic organisms such as shellfish and crustaceans are attached is 30% or more but less than 70% of the area on the coating surface before being placed in seawater. C: On the coating surface after being placed in the sea, the area on which three attached aquatic organisms such as shellfish and crustaceans are attached is 70% or more of the area on the coating surface before being placed in seawater. A grade of B or above is acceptable, with A being preferable to B.

[0082] Water-Resistant Adhesion Test: Each of the coating compositions of Examples 1 to 6, 9 to 13, and Comparative Examples 1 and 2 was applied to the substrates listed in Table 1 using an applicator to a dry film thickness of 200 μm. The coating was then dried at room temperature for 24 hours and then at 70°C for 1 hour to prepare water-resistant adhesion test panels. Each of the resulting water-resistant adhesion test panels was immersed in tap water at 23°C for 12 days, removed, and then dried at room temperature for 6 hours. One hundred 2 mm x 2 mm square grids were created according to JIS K 5600-5-6 (1990). Adhesive tape was applied to the surface and the remaining state of the grid coating film after rapid peeling was examined. Water-resistant adhesion was evaluated according to the following criteria. Example 7, in which no grid grid could be created, and Example 8 and Comparative Example 3, which lacked a coating film, were not evaluated. Grades S, A, and B were considered acceptable, with A being preferred over B, and S being the most preferable. The evaluation results are also shown in Table 1. S: 100 grid-like paint films remain, and no chipping of the edges has occurred. A: 100 grid-like paint films remain, and chipping of the edges has occurred. B: 99 or fewer grid-like paint films remain, and some are still attached. C: The entire surface has peeled off.

Claims

1. A composition for preventing the fouling of shellfish and crustaceans, comprising at least one resin component and an iron source chelated with humic acid.

2. A composition for preventing adhesion of shellfish and crustaceans as described in claim 1, wherein the resin component is at least one resin component selected from the group consisting of polyester resin, polyolefin resin, polyamide resin, alkyd resin, acrylic resin, epoxy resin, amino resin, fluororesin, silicone resin, urethane resin, vinyl resin, cellulose resin, and copolymers containing these.

3. A composition for preventing the adhesion of shellfish and crustaceans according to claim 1, wherein said humic acid is fulvic acid.

4. The composition for preventing the adhesion of shellfish and crustaceans according to claim 3, further comprising soluble silica.

5. A composition for preventing the adhesion of shellfish and crustaceans as described in claim 4, wherein the humic acid-chelated iron source and / or soluble silica have a d50 (volume average particle size) in the range of 0.01 to 300 μm.

6. A method for preparing a composition for preventing the fouling of shellfish and crustaceans, comprising the step of mixing at least one resin component with an iron source chelated with humic acid.

7. The method according to claim 6, wherein the resin component is at least one resin component selected from the group consisting of polyester resins, polyolefin resins, polyamide resins, alkyd resins, acrylic resins, epoxy resins, amino resins, fluororesins, silicone resins, urethane resins, vinyl resins, cellulose resins, and copolymers containing any of these.

8. The method of claim 7, wherein the humic acid chelated iron source is a fulvic acid iron silica material.

9. The method according to claim 8, wherein the fulvic acid iron silica material is fulvic acid iron containing soluble silica, produced by mixing 50 mg to 7000 mg of polysilica iron liquid (PSI) with 1 kg of a fermented product produced by fermenting and sterilizing sewage sludge and wood chips to produce fulvic acid, and then aging the mixture.

10. A coating composition for preventing adhesion of shellfish and crustaceans, comprising the composition according to any one of claims 1 to 5.

11. A film for preventing adhesion of shellfish and crustaceans, comprising the composition according to any one of claims 1 to 5.

12. A resin molded article for preventing adhesion of shellfish and crustaceans, comprising the composition according to any one of claims 1 to 5.

13. A method for preventing the attachment of shellfish and crustaceans to a substrate, comprising the steps of: applying the composition according to any one of claims 1 to 5 to the substrate; and drying the composition applied in the above step to form a film.