Method for producing a composition for preventing adhesion of shellfish and crustaceans

Abstract

To provide a novel method for producing a composition for preventing adhesion of shellfish and crustaceans. 【Solution means】A method for producing a composition for preventing adhesion of shellfish and crustaceans, comprising a step of mixing at least one resin component and a fulvic acid iron silica material, wherein the resin component is a polyester resin, a polyolefin resin, a polyamide resin, an alkyd resin, an acrylic resin, an epoxy resin, an amino resin, a fluororesin, a silicone resin, a urethane resin, a vinyl resin, a cellulose resin, and at least one resin component selected from the group consisting of copolymers containing these, and the fulvic acid iron silica material is a fulvic acid iron containing soluble silica produced by aging by mixing a polysilicate iron liquid agent (PSI) in the range of 50 mg to 7000 mg with respect to 1 kg of a fermentation product in which fulvic acid is produced by fermentation and sterilization treatment of sewage sludge and wood chips.

Description

Technical Field

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

Background Art

[0002] Shellfish and crustaceans such as barnacles and mussels attach to the bottom of ships and the like, greatly reducing their functions. For example, when these shellfish and crustaceans attach to and accumulate on a ship, unevenness occurs on the surface of the ship's bottom, reducing the propulsion force. Shellfish and crustaceans that attach to the target in this way are called marine fouling organisms, and countermeasures for preventing their attachment have been studied. However, the development of new anti-attachment methods is still eagerly desired.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0005] Under such circumstances, as a result of intensive studies by the present inventors, for 1 kg of a fermentation product in which fulvic acid is produced by the fermentation and sterilization treatment of sewage sludge and wood chips, a polysilicate iron solution (PSI) is mixed in the range of 50 mg to 7000 mg and aged, and the fulvic acid iron silica material containing soluble silica produced thereby is used. It has been found that the adhesion to shellfish and crustaceans can be suppressed by using a composition obtained by a method including a step of mixing 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 with the fulvic acid iron silica material. The present invention is based on such new findings. Accordingly, the present invention provides the following items: Item 1. A method for producing a composition for preventing the adhesion of shellfish and crustaceans, comprising a step of mixing at least one resin component and a fulvic acid iron silica material, 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, and the fulvic acid iron silica material is fulvic acid iron containing soluble silica produced by mixing a polysilicate iron solution (PSI) in the range of 50 mg to 7000 mg with respect to 1 kg of a fermentation product in which fulvic acid is produced by the fermentation and sterilization treatment of sewage sludge and wood chips and aging.

[0006] Item 2. A film for preventing the adhesion of shellfish and crustaceans, containing the composition obtained by the method according to Item 1.

[0007] Item 3. A resin molded article for preventing the adhesion of shellfish and crustaceans, containing the composition obtained by the method according to Item 1.

[0008] Item 4. The method according to Item 1, the film according to Item 2, or the resin molded body according to Item 3, wherein the amount of the ferric fulvate silica material is 0.01 to 10 parts by mass with respect to 1 part by mass of the solid content of the resin component.

Effect of the Invention

[0009] According to the present invention, it is possible to provide a novel method for producing a composition for preventing the adhesion of shellfish and crustaceans. Further, the composition obtained by the method of the present invention can be applied to objects of various shapes to form a film, and resin molded bodies of various shapes can also be produced using the composition itself. Therefore, according to the present invention, it is possible to perform treatment for preventing the adhesion of shellfish and crustaceans in various places.

Embodiments for Carrying Out the Invention

[0010] The present invention is a method for producing a composition for preventing the adhesion of shellfish and crustaceans, including a step of mixing at least one resin component and a ferric fulvate 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 these, and the ferric fulvate silica material is ferric fulvate containing soluble silica produced by mixing a polysilicate iron liquid agent (PSI) in the range of 50 mg to 7000 mg with respect to 1 kg of a fermentation product in which fulvic acid is produced by fermentation and sterilization treatment of sewage sludge and wood chips, and aging. A method is provided.

[0011] The shellfish and crustaceans to be targeted for adhesion prevention according to the present invention are not particularly limited. For example, as shellfish, there are those of the genus Mytilus (Mytilus edulis, Mytilus trossulus, Mytilus galloprovincialis, Mytilus coruscus, Mytilus edulis platensis, etc.), those of the genus Septifer (Septifer virgatus, etc.), those of the genus Pinctada (Pinctada fucata, Pinctada martensii, Pinctada maxima, etc.), those of the genus Scapharca (Scapharca broughtonii, etc.), those of the genus Modiolus (Modiolus kurilensis, Modiolus philippinarum, etc.); and shellfish such as oysters. As crustaceans, there are those such as barnacles, etc.

[0012] At least one resin component Examples of the resin include polyester resins, polyolefin resins, polyamide resins, alkyd resins, acrylic resins, epoxy resins, amino resins, fluororesins, silicone resins, urethane resins, vinyl resins, cellulose resins, copolymers containing these, and the like. These resins can be used alone or in combination of two or more.

[0013] As the polyester resin, polymers having an ester bond can be widely used. For example, polyester polyols and the like can be mentioned. Examples of the polyester polyol include those obtained by polycondensation of a low molecular weight diol and a dibasic acid, those obtained by ring-opening reaction of a lactone compound using a low molecular weight diol as an initiator, and the like.

[0014] 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 - C22) diol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, cyclohexanedimethanol, alkane - 1,2 - diol (C17 - C20), hydrogenated bisphenol A, 1,4 - dihydroxy - 2 - butene, 2,6 - dimethyl - 1 - octene - 3,8 - diol, bis - hydroxyethoxybenzene, xylene glycol, bis - 2 - hydroxyethylene terephthalate and other low molecular weight diols.

[0015] Examples of the dibasic acid include adipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, etc. The low molecular weight diol and the dibasic acid can be used alone or in combination of two or more.

[0016] In the latter case, examples of the lactone compound include ε - caprolactone, polyβ - methyl - δ - valerolactone, etc. Examples of the alkyd resin 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 a method known per se. Although it is not possible to strictly distinguish between drying oil fatty acids and semi - drying oil fatty acids, usually, drying oil fatty acids are unsaturated fatty acids with an iodine value of 130 or more, and semi - drying oil fatty acids are unsaturated fatty acids with an iodine value of 100 or more and less than 130. On the other hand, non - drying oil fatty acids are usually fatty acids with an iodine value of less than 100.

[0017] Examples of the 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, eno oil fatty acids, hemp seed oil fatty acids, grape seed 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.

[0018] Examples of the above acid components include benzoic acid, p-tert-butylbenzoic acid, (anhydrous) phthalic acid, hexahydro(anhydrous)phthalic acid, tetrahydro(anhydrous)phthalic acid, tetrachloro(anhydrous)phthalic acid, hexachloro(anhydrous)phthalic acid, tetrabromo(anhydrous)phthalic acid, trimellitic acid, "Hyemic acid" [product of Hitachi Chemical Co., Ltd.; "Hyemic acid" is a registered trademark of the company.], (anhydrous) succinic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, adipic acid, sebacic acid or oxalic acid, and combinations thereof.

[0019] In addition, saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid, and non-drying oil fatty acids such as hydrogenated coconut oil fatty acids, coconut oil fatty acids, and palm oil fatty acids can also be used in combination as the acid component. These acid components can be used alone or in combination of two or more.

[0020] Examples of the above alcohol components 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.

[0021] 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.

[0022] Examples of the polyolefin resin include a radical homopolymer or copolymer of at least one olefin selected from, for example, ethylene, propylene, butene, methylbutene, isoprene, etc., and a radical copolymer of the olefins and vinyl acetate, butadiene, acrylate ester, methacrylate ester, etc.

[0023] Examples of the acrylic resin include a resin formed by copolymerizing a polymerizable unsaturated monomer component containing a (meth)acryloyl compound as an essential component and other polymerizable unsaturated monomers.

[0024] Examples of the (meth)acryloyl compound include linear or branched alkyl (meth)acrylates such as 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 highly branched long-chain alkyl acrylate); 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; phosphate group-containing (meth)acrylates such as (2-(meth)acryloyloxyethyl) acid phosphate and (2-(meth)acryloyloxypropyl) acid phosphate; 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, 1,1,1-trishydroxymethylpropane tri(meth)acrylate; Oxidation-curable group-containing (meth)acryloyl monomers such as dicyclopentenyl oxyethyl (meth)acrylate, dicyclopentenyl oxypropyl (meth)acrylate, dicyclopentenyl (meth)acrylate; 1,2,2,6,6-pentamethylpiperidyl (meth)acrylate, 2,2,6,6-tetramethylpiperidinyl (meth)acrylate; Quaternary ammonium base-containing (meth)acrylates such as 2-((meth)acryloyloxy)ethyltrimethylammonium chloride, 2-((meth)acryloyloxy)ethyltrimethylammonium bromide, (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminopropyltrimethylammonium bromide, tetrabutylammonium (meth)acrylate, tetramethylammonium (meth)acrylate, trimethylbenzylammonium (meth)acrylate, 2-((meth)acryloyloxy)ethyltrimethylammonium dimethyl phosphate; (meth)acrylates having a polyoxyalkylene chain with an alkoxy group at the molecular end; Examples thereof include, and these can be used alone or in combination of two or more thereof.

[0025] In addition, examples of 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 acetoacetoxyallyl ester; 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; oxidation-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; fluorovinyl ethers such as fluoroalkyl trifluorovinyl ether and perfluoroalkyl trifluorovinyl ether, etc. Examples thereof include, and these can be used alone or in combination of two or more thereof.

[0026] In addition, the at least one resin component may include a chlorinated resin. Examples of the chlorinated resin include vinyl chloride resins, chlorinated rubber resins, chlorinated polyethylene resins, chlorinated polypropylene resins, vinyl chloride-vinyl isobutyl ether copolymers, vinyl chloride-vinyl acetate copolymers, etc., and chlorinated copolymer resins are preferred. Examples of the chlorinated copolymer resin include vinyl chloride-vinyl acetate copolymers, etc. In the present invention, the "vinyl chloride-vinyl acetate copolymer" includes not only a copolymer of vinyl chloride and vinyl acetate (vinyl chloride-vinyl acetate copolymer), but also a copolymer containing monomers other than vinyl chloride and vinyl acetate as raw materials (for example, vinyl chloride-vinyl acetate-maleic acid copolymer, vinyl chloride-vinyl acetate-(meth)acrylic acid-(meth)acrylate copolymer, etc.). These chlorinated resins can be used alone or in combination of two or more. In this specification, "(meth)acrylate" means acrylate and / or methacrylate, and "(meth)acrylic acid" refers to acrylic acid and / or methacrylic acid. "(meth)acryloyl" refers to acryloyl and / or methacryloyl. "(meth)acrylamide" refers to acrylamide and / or methacrylamide.

[0027] The weight average molecular weight of these resins is not limited, but from the viewpoints of film-forming properties and coating film strength, for example, those in the range of 10,000 to 300,000, preferably 30,000 to 200,000, more preferably 50,000 to 100,000 can be mentioned.

[0028] Ferric fulvate silica material In this specification, fulvic acid refers to a component among the components constituting humic substances that dissolves in alkali and also dissolves in acid. The molecular weight of fulvic acid is not limited, but for example, those having a weight average molecular weight of less than 10,000 (for example, 7000 or less, 5000 or less, 3000 or less, etc.) can be mentioned. Here, humic substances refer to products obtained by decomposition of dead plants, animal carcasses, etc. in soil by microorganisms. Humic substances usually contain various organic compounds.

[0029] In the present invention, the fulvic acid iron silica material can be produced by mixing a polysilicate iron solution (PSI) in the range of 50 mg to 7000 mg with respect to 1 kg of a fermentation product in which fulvic acid is produced by the fermentation and sterilization treatment of sewage sludge and wood chips, and aging. The production of the fulvic acid iron silica can be carried out according to the method described in Patent Document 2. Specifically, for example, it is as follows.

[0030] In the present invention, as the object to which the polysilicate iron solution (PSI) is added, a fermentation product obtained by the fermentation and sterilization treatment of sewage sludge and wood chips can be used. For example, in the fermentation process for preparing the above fermentation product, harmful microorganisms can be killed or inactivated by adjusting the fermentation temperature and time.

[0031] As the polysilicate iron solution (PSI), a commercially available one can be appropriately used. By using a polysilicate iron solution (PSI) mainly composed of iron and silica, soluble silica and iron can be supplied, and soluble silica and fulvic acid iron can be easily eluted into water and soil, which is preferable.

[0032] The addition amount of the polysilicate iron solution (PSI) to the above fermentation product is 50 mg / kg to 7000 mg / kg per kg of the mass of the fermentation product, preferably 500 mg / kg to 5000 mg / kg. From the viewpoint of suppressing the adhesion of marine fouling organisms, the above range is preferable. Also, in terms of the silica iron (FeCl3 + Na2O·nSiO2·xH2O) conversion contained in the polysilicate iron solution (PSI), it is preferable to add PSI so that it is preferably 3.5 mg / kg to 2030 mg of silica iron / kg of the fermentation product, more preferably 7 mg / kg to 1450 mg of silica iron / kg of the fermentation product per kg of the mass of the fermentation product.

[0033] In the present invention, the d50 (volume average particle diameter) of the ferric fulvate silica material is not limited, and for example, it is 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 adhesion resistance, the above range is preferable. The d50 (volume average particle diameter) indicates the median diameter, and more specifically, it is the particle diameter at which the cumulative particle diameter distribution from the small particle diameter side becomes 50% in the particle size distribution based on volume. In the present invention, the d50 (volume average particle diameter) can be measured by measuring the volume-based particle size distribution by the laser diffraction scattering method using a submicron particle size distribution measuring device "Microtrac MT3000" (trade name, manufactured by Microtrac Bell).

[0034] The content ratio of the iron component and silica in the ferric fulvate silica material is not limited. For example, with respect to 1 part by mass of the former, the latter is 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass. In this specification, the content of the "iron component" means the total content of iron ions released from iron and iron compounds (such as iron oxide) contained in the ferric fulvate silica material. Also, the content ratio of the iron component and fulvic acid in the ferric fulvate silica material is not limited. For example, with respect to 1 part by mass of the former, the latter is 30 to 90 parts by mass, preferably 45 to 75 parts by mass.

[0035] Mixing process The method of the present invention includes a step of mixing the at least one resin component (hereinafter simply referred to as the resin component unless otherwise specified, which is the resin component described in the section of the "at least one resin component").) and the ferric fulvate silica material.

[0036] In the present invention, the blending ratio of the resin component and the ferric fulvate silica material obtained by the above step is not limited. For example, with respect to 1 part by mass of the former, the latter can be used in the 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. From the viewpoint of crack resistance, it is preferable that the blending ratio of the resin component and the ferric fulvate silica material obtained by the above step is within the above range.

[0037] The mixing of the resin component and the ferric fulvate silica material can be carried out using a method known per se. For example, a disper, 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.

[0038] In the step of mixing the resin component and the ferric fulvate silica material in the present invention, the resin component may be used in a state of being mixed with other raw materials. Also, the ferric fulvate silica material may be used in a state of being mixed with other raw materials. Therefore, in the present invention, the step of "mixing at least one resin component and a ferric fulvate silica material" is not limited as long as the resin component and the ferric fulvate silica material are mixed, and may be any of mixing only the resin component and only the ferric fulvate silica material; mixing a mixture containing the resin component and other raw materials with the ferric fulvate silica material; mixing the resin component with a mixture containing the ferric fulvate silica material and other raw materials; and mixing a mixture containing the resin component and other raw materials with a mixture containing the ferric fulvate silica material and other raw materials.

[0039] Examples of raw materials other than the resin component and the fulvic acid iron silica material include, for example, plasticizers. Examples of plasticizers include phosphate esters (e.g., tricresyl phosphate), chlorinated paraffins (e.g., chlorinated normal paraffin), liquid paraffin, n-paraffin, phthalic acid esters (e.g., isodecyl phthalate), polyester resins (e.g., Polysizer P-29 manufactured by Dainippon Ink and Chemicals, Inc.), epoxidized oils (e.g., Adekaizer O-130P, epoxidized soybean oil manufactured by Adeka Argus Chemical Co., Ltd.), polybutene, terpene phenol, polyvinyl ethyl ether, and the like. These plasticizers can be used alone or in combination of two or more. When using a plasticizer, the amount used is not limited, but for example, 0.001 to 1 part by mass, preferably 0.01 to 0.5 part by mass of the plasticizer can be used with respect to 1 part by mass of the resin component.

[0040] In addition, thickeners and the like may be used as raw materials other than the resin component and the fulvic acid iron silica material. Examples of thickeners include organic thickeners such as oxidized polyethylene wax, polyethylene wax, fatty acid amide wax, castor oil wax, and dimer acid ester; 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 of two or more. Also, for the addition of thickeners, commercially available products such as DISPARLON NS-30 (containing oxidized polyethylene and fatty acid amide wax) can be used. When using a thickener, the amount used is not limited, but for example, 0.001 to 0.5 part by mass, preferably 0.01 to 0.3 part by mass of the thickener component can be used with respect to 1 part by mass of the resin component.

[0041] In addition, as raw materials other than the resin component and the fulvic acid iron silica material, a solvent may be used. Examples of the solvent 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 can be used alone or in combination of two or more. When using a solvent, its usage amount is not limited. For example, 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass of the solvent can be used with respect to 1 part by mass of the resin component.

[0042] As raw materials other than the resin component and the fulvic acid iron silica material, for example, nutritional components and the like may be used. Examples of the above nutritional components include nitrogen-containing substances, phosphorus-containing substances, alkali metal-containing substances, alkaline earth metal-containing substances, etc., which are generally known as fertilizers for cultivated plants and are effective as nutritional components of seaweeds. Among these substances, there may also be included substances containing two or more of the above atoms, which contain nitrogen, calcium, and trace amounts of other atoms (for example, phosphorus) in combination, such as lime nitrogen, bone meal, and oyster shell powder. More specifically, the following can be mentioned. Nitrogen-containing substances (such as ammonium sulfate, urea, calcium cyanamide, ammonium chloride, ammonium nitrate, ammonium phosphate, metal salts of ethylenediaminetetraacetic acid (EDTA), defatted soy powder, chicken manure, cow manure, amino acid salts, guanylurea salts, guanidine salts, oil cake, glyoxime, chemical fertilizers, etc.), phosphorus-containing substances (such as superphosphate of lime, triple superphosphate of lime, metaphosphate of lime, ammonia triple superphosphate of lime, soluble phosphate fertilizers, condensed phosphates, etc.), alkali metal-containing substances (such as potassium chloride, potassium phosphate, potassium sulfate, potassium nitrate, seaweed ash, plant ash, etc.), alkaline earth metal-containing substances (such as oyster shell organic lime, bone meal, fish meal, oyster shell powder, crab shell powder, calcium carbonate, etc.), etc. For the nutritional components containing the above atoms in combination, for convenience, they are listed representatively in the substance names containing one atom. Each of the substances exemplified above is a part of the nutritional components that can be used in the present invention. As long as it is a fertilizer substance or a nutritional component that contains the above atoms alone or in combination, those other than the above-exemplified ones can be used without particular limitation. These nutritional components can be used alone or in combination of two or more. Among these substances, one kind, preferably two or more kinds of nutritional components selected from nitrogen-containing substances and alkaline earth metal-containing substances are preferably used. There is no particularly strict limitation on the combined ratio of these when using two or more nutritional components in combination. When using nutritional components, the amount used is not limited. For example, 0.1 to 5 parts by mass, preferably 0.3 to 3 parts by mass of nutritional components can be used with respect to 1 part by mass of the resin component. By applying the composition of the present invention to an article to which a material for promoting the growth of algae is added, the adhesion of shellfish and crustaceans to the article can be prevented, contributing to an efficient increase in blue carbon. In particular, it is preferable to blend nutritional components in such an embodiment.

[0043] Furthermore, in the composition for preventing the adhesion of the above shellfish and crustaceans, in addition to the above substances, for the purpose of adjusting paint viscosity, storage stability, painting workability, color tone, antifouling property, and further the state of the paint film and its physical properties, known additives, curing accelerators, antifouling agents, coloring pigments, etc. usually used in paints can also be used.

[0044] 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. The material of the substrate is not limited, and examples include resins (such as vinyl chloride, polyester, acrylic, FRP, etc.), metals (such as steel, aluminum, stainless steel, etc.), concrete, rock, wood, fiber, biodegradable fiber, and those with metal coated with resin. Resins, those with metal coated with resin, or concrete, etc. 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 for applying the coating composition to the substrate is not limited, and for example, an applicator, a bar coater, a spray, dipping, a roller, a brush, flow coating, etc. can be used. The thickness of the coating film is not limited, but it can be set in the range of, for example, 50 to 3,000 μm, preferably 100 to 1,000 μm in terms of dry film thickness. Examples of the substrate include the bottom of a ship, fishing nets, fishing gear, buoys, seawater desalination facilities, water intake pits such as those in thermal power plants, seawater cooling water facilities using seawater in power plants, scaffolds for growing algae, etc. Therefore, in one embodiment, the present invention provides a film for preventing the attachment of shellfish and crustaceans, containing the composition obtained by the above method. In this embodiment, examples of the film of the present invention include the composition obtained by the above method in a dried and / or cured state.

[0045] Also, in one embodiment, by producing a resin molded body using the composition itself obtained by the above method, a resin molded body with suppressed attachment of shellfish and crustaceans can be obtained. Therefore, the present invention provides a resin molded body for preventing the attachment of shellfish and crustaceans, containing the composition obtained by the above method. The production of the resin molded body can be carried out using a molding method known per se (such as injection molding, compression molding, extrusion molding, blow molding, foam molding, etc.) other than using the composition obtained by the above method.

Examples

[0046] Hereinafter, the present invention will be described in more detail with reference to examples, but it is not limited thereto.

[0047] Comparative Example 1 Vinyl chloride - vinyl acetate copolymer resin "SOLBIN AL" (vinyl chloride / vinyl acetate / vinyl alcohol = 92.5 / 2.5 / 5, degree of polymerization 300, molecular weight Mw = 5.3x10 4 manufactured by Nissin Chemical Industry Co., Ltd., 113 g) was dissolved in 230 g of methyl isobutyl ketone and 230 g of "mixed xylene" (xylene - ethylbenzene mixture) manufactured by Maruzen Petrochemical Co., Ltd., and mixed and dispersed at a stirring speed of about 2,000 rpm using a disper to prepare the paint composition of Comparative Example 1.

[0048] The obtained paint composition was applied to a transparent vinyl chloride plate with a width of 200 mm, a length of 300 mm, and a thickness of 2.0 mm using a bar coater to a dry film thickness of 300 μm, and left at room temperature for 3 days or more to dry the solvent to form a coating film, and a test plate for marine evaluation was prepared.

[0049] Example 1 Vinyl chloride - vinyl acetate copolymer resin "SOLBIN AL" (vinyl chloride / vinyl acetate / vinyl alcohol = 92.5 / 2.5 / 5, degree of polymerization 300, molecular weight Mw = 5.3x10 4 manufactured by Nissin Chemical Industry Co., Ltd., 113 g) was dissolved in 230 g of methyl isobutyl ketone and 230 g of "mixed xylene" (xylene - ethylbenzene mixture) manufactured by Maruzen Petrochemical Co., Ltd., and 1402 g of the following formulation was mixed and dispersed in the solution at a stirring speed of about 2,000 rpm using a disper to prepare the paint composition of Example 1. Except for using the paint composition obtained above, in the same manner as in Comparative Example 1, a coating film on a rigid vinyl chloride plate was formed, and a test plate for marine evaluation was prepared.

[0050] Example 2 113 g of acrylic resin PARALOID B-44 Resin (solid content 100%) manufactured by DOW Co., Ltd. was dissolved in 230 g of methyl isobutyl ketone and 230 g of "mixed xylene" (xylene / ethylbenzene mixture) manufactured by Maruzen Petrochemical Co., Ltd. To this solution, 1402 g of the formulation shown below was mixed and dispersed using a disperser at a stirring speed of about 2,000 rpm to prepare the coating composition of Example 2. Except for using the coating composition obtained above, in the same manner as in Comparative Example 1, a coating film was formed on a rigid PVC plate to prepare a test plate for marine evaluation.

[0051] Example 3 141 g of polyester polyol resin XR-1016 (solid content 80%, hydroxyl value 70 mg KOH / g) manufactured by ToShin YuShi Co., Ltd. was dissolved in 216 g of methyl isobutyl ketone and 216 g of "mixed xylene" (xylene / ethylbenzene mixture) manufactured by Maruzen Petrochemical Co., Ltd. To this solution, 1402 g of the formulation shown below was mixed and dispersed using a disperser at a stirring speed of about 2,000 rpm to prepare the coating composition of Example 3. Except for using the obtained coating composition, in the same manner as in Comparative Example 1, a coating film was formed on a rigid PVC plate to prepare a test plate for marine evaluation. (Formulation 1) The fulvic acid iron silica material "Ryugu no Tsukai" manufactured by Koyo Co., Ltd. was prepared by the following method. "Ryugu no Tsukai" was produced by spraying and mixing 5 kg of a silica iron-based liquid substance (PSI-025 manufactured by Taiki Chemical Industry Co., Ltd.) onto 10 tons of the fermented product of a mixture of sewage sludge and wood chips, and aging in a warehouse for 20 days. The composition of the silica iron-based liquid substance (PSI-025) is as follows. Iron(III) chloride (FeCl3) 5 - 27 wt / wt% Sodium silicate (Na2O·nSiO2·xH2O (n = about 3) 2 wt / wt% (as SiO2) Sulfuric acid 1 wt / wt% Water 70 - 92 wt / wt%. 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 are those of the filtrate obtained by filtering 50 g of "Ryugu no Tsukai" through a 5A filter paper after storing it at room temperature for 20 days in 100 ml of deionized water. Fulvic acid and soluble iron were analyzed by Japan Food Function Analysis Laboratory Co., Ltd. Available silica was analyzed using an ICP-MS analyzer at Kurume Research Park Co., Ltd. The obtained "Ryugu no Tsukai" was coarsely pulverized with a 10 L Henschel mixer under stirring conditions of 2000 rpm for 10 seconds, and then finely pulverized with an atomizer FA-SW-1 type at a main rotor inverter frequency setting of 45 Hz (= 1350 rpm) in one pass. This pulverized product was sieved with a sieve having an aperture of 150 mesh using a vibrating sieve machine to obtain Formulation 1. The particle size distribution of the obtained Formulation 1 was measured with a laser diffraction / scattering particle size distribution measuring device.

[0052] Example 4 and Comparative Examples 2 to 4 Except for using the formulations shown in Table 1, paint compositions of Example 4 and Comparative Examples 2 to 4 were obtained in the same manner as in Example 1. Formulations 2 and 3 were prepared as follows. (Formulation 2) Formulation 2 was obtained in the same manner as Formulation 1, except that the fulvic acid iron material "Granular Fulvoiron" manufactured by PIIA BIO was used instead of the fulvic acid iron silica material "Ryugu no Tsukai" manufactured by Koyo Co., Ltd. The above "Granular Fulvoiron" does not contain silica. (Formulation 3) Formulation 3 was obtained in the same manner as Formulation 1, except that the fulvic acid iron and silicon material "Chelate Marine K1 type" manufactured by Nichimaru Sangyo Co., Ltd. was used instead of the fulvic acid iron silica material "Ryugu no Tsukai" manufactured by Koyo Co., Ltd. "Chelate Marine K1 type" contains silicon, but it was not obtained by a method including a step of mixing a polysilicate iron liquid agent (PSI) in the range of 50 mg to 7000 mg with 1 kg of a fermentation product in which fulvic acid was generated by fermentation and sterilization treatment of sewage sludge and wood chips, and aging.

[0053]

Table 1

[0054] In the above table, the examples and comparative examples in which the "base material" column is described as "-" indicate that a resin molded body was produced with each composition.

[0055] Example 5 A paint composition was obtained in the same manner as in Example 1, except that the composition described in Table 1 was used. A polyethylene terephthalate net as a base material was prepared. The obtained paint composition was immersed in the net, and after lifting the net from the paint, excess paint was removed, air-dried, and then fixed to an iron frame of 35 cm × 45 cm.

[0056] Example 6 70 g of a polypropylene resin with an MFR (temperature 230 °C, load 2.16 kg) of 45 g / 10 minutes and 30 g of Formulation 1 were mixed. The obtained mixture was melt-kneaded using a twin-screw kneading extruder, and after extruding the melt-kneaded product in a strand shape, it was cut to produce resin pellets. The resin pellets were injection-molded using an injection molding machine to produce a sheet having a length of 300 mm, a width of 200 mm, and a thickness of 1 mm, which was used as a test plate for marine evaluation according to the implementation. Examples 7 and 8 Except for the formulation in Table 1, paint compositions of Examples 7 and 8 were obtained in the same manner as in Example 1. Except for using the obtained paint composition, a coating film on a rigid PVC plate was formed in the same manner as in Comparative Example 1 to produce a test plate for marine evaluation.

[0057] Comparative Example 5 A sheet was produced in the same manner as in Example 6 using only a polypropylene resin not containing Formulations 1 to 3, and used as a test plate for marine evaluation of the comparative example.

[0058] Marine evaluation test The test plates for marine evaluation thus produced were fixedly installed using piles in the tidal flat 100 m off the coast of Nagashima-cho, Tamana-gun, Kumamoto Prefecture. The average tidal level of this test site is about 3 to 4 m, and the maximum tidal level is 5 to 6 m. Three months after installation, a crack resistance test and an antifouling performance test were conducted. · Crack resistance test: The coated film was visually observed on the test piece to examine the presence or absence of crack generation. S: No crack was observed. A: Fine cracks were observed in a partial range of the coated film surface. B: Fine or distinct cracks were observed in a wide range of the coated film surface. C: Cracks reaching the substrate were observed. Grade B or above is considered passing, grade A is preferred over grade B, and grade S is the most preferred. · Antifouling performance test A: On the surface of the coated film after being immersed in the sea, the area where attached aquatic organisms such as shellfish and crustaceans adhere is less than 30% of the surface before being immersed in seawater. B: On the surface of the coated film after being immersed in the sea, the area where attached aquatic organisms such as shellfish and crustaceans adhere is 30% or more and less than 70% of the coated film surface before being immersed in seawater. C: On the surface of the coated film after being immersed in the sea, the area where attached aquatic organisms such as shellfish and crustaceans adhere is 70% or more of the coated film surface before being immersed in seawater. Grade A or above is considered passing.

[0059] Water resistance adhesion test The paint compositions of Examples 1 to 4, 7 and 8, and Comparative Examples 1 to 4 were each applied to a transparent vinyl chloride plate with a width of 200 mm, a length of 300 mm and a thickness of 2.0 mm made of rigid PVC by an applicator so that the dry film thickness became 200 μm. Then, it was dried at room temperature for 24 hours and further dried at 70 °C for 1 hour to obtain each test plate for water resistance adhesion. After each obtained test plate for water resistance adhesion was immersed in running water at 23 °C for 12 days and then pulled out, it was dried at room temperature for 6 hours. According to JIS K 5600-5-6 (1990), 100 grids of 2 mm × 2 mm were made, an adhesive tape was attached to the surface, and after being rapidly peeled off, the remaining state of the grid coated film was examined, and the water resistance adhesion was evaluated according to the following criteria. For Example 5 in which grids could not be made, and Examples 6 and Comparative Example 5 in which there was no coated film, no evaluation was performed. Grade S, A, and B are considered passing, grade A is preferred over grade B, and grade S is the most preferred. The evaluation results are shown in Table 1 together. S: There are 100 remaining goban-pattern coatings and no edge overhangs A: There are 100 remaining goban-pattern coatings and edge overhangs have occurred B: The remaining number of goban-pattern coatings is 99 or less and some are adhered C: The entire surface has peeled off

Claims

1. 1. A method for producing a composition for preventing the fouling of shellfish and crustaceans, comprising the steps of mixing at least one resin component with an iron silica fulvic acid material, 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-based resins, vinyl-based resins, and cellulose-based resins; The method is characterized in that 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.

2. 13. A method for producing a film for preventing adhesion of shellfish and crustaceans, comprising the steps of applying to a substrate the composition obtained by the method according to claim 1, and drying and / or curing the applied composition.

3. A method for producing a resin molded article for preventing adhesion of shellfish and crustaceans, comprising a step of molding the composition obtained by the method according to claim 1 by at least one method selected from the group consisting of injection molding, compression molding, extrusion molding, blow molding and foam molding.

4. The method according to claim 1, wherein the amount of the fulvic acid iron silica material is 0.01 to 10 parts by mass per 1 part by mass of the resin component solid content.

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