Composition for preventing attachment of shellfish and crustaceans

Abstract

To provide a novel composition for preventing the adhesion of shellfish and crustaceans. 【Solution means】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.

Description

Technical Field

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

Background Art

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

Means for Solving the Problems

[0005] Under such circumstances, as a result of intensive studies by the present inventors, it has been found that the adhesion of shellfish and crustaceans to the target can be suppressed by using a composition containing at least one resin component and an iron supply material chelated with humic acid. The present invention is based on such novel findings. Therefore, the present invention provides the following items: 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 attachment 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 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.

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

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

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

[0010] Item 6. A paint composition for preventing attachment of shellfish and crustaceans, containing the composition according to any one of Items 1 to 5.

[0011] Item 7. A film for preventing attachment of shellfish and crustaceans, containing the composition according to any one of Items 1 to 5.

[0012] Item 8. A resin molded article for preventing attachment of shellfish and crustaceans, containing the composition according to any one of Items 1 to 5.

Advantages of the Invention

[0013] According to the present invention, a novel composition for preventing attachment of shellfish and crustaceans can be provided. Further, the composition of the present invention can also be applied to objects of various shapes to form a film, and can also be used to manufacture resin molded articles of various shapes using the composition itself. Therefore, according to the present invention, it is possible to perform treatment for preventing attachment of shellfish and crustaceans at various locations.

BEST MODE FOR CARRYING OUT THE INVENTION

[0014] The present invention provides a composition for preventing the attachment of shellfish and crustaceans, which contains at least one resin component and an iron supply material chelated with humic acid.

[0015] The shellfish and crustaceans to be prevented from attaching according to the present invention are not particularly limited. For example, as shellfish, there are genus Mytilus (Mytilus edulis, Mytilus trossulus, Mytilus galloprovincialis, Mytilus coruscus, Mytilus edulis platensis, etc.), genus Semimytilus (Semimytilus algosus, etc.), genus Pinctada (Pinctada fucata, Pinctada martensii, etc.), genus Isognomon (Isognomon isognomum, etc.), genus Modiolus (Modiolus kurilensis, Modiolus philippinarum, etc.); and shellfish such as oysters. As crustaceans, there are barnacles, etc.

[0016] 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, and copolymers containing these. These resins can be used alone or in combination of two or more.

[0017] As the polyester resin, a polymer having an ester bond can be widely used. For example, polyester polyols can be mentioned. Examples of the polyester polyol 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.

[0018] In the former case, examples of the low molecular weight diol include ethylene glycol, propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 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.

[0019] 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.

[0020] In the latter case, examples of the lactone compound include ε-caprolactone, poly-β-methyl-δ-valerolactone, etc.

[0021] 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 drying oil fatty acids and semi-drying oil fatty acids cannot be strictly distinguished, 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.

[0022] 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 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.

[0023] 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, "Hy Mic acid" [product of Hitachi Chemical Co., Ltd.; "Hy Mic 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.

[0024] In addition, as acid components, 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. These acid components can be used alone or in combination of two or more.

[0025] 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.

[0026] 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.

[0027] Examples of the polyolefin resin include a radical homopolymer or copolymer of at least one olefin selected from ethylene, propylene, butene, methylbutene, isoprene, etc., and a radical copolymer of the olefins and vinyl acetate, butadiene, acrylate ester, methacrylate ester, etc.

[0028] Examples of the acrylic resin include a resin formed by copolymerizing a polymerizable unsaturated monomer component containing a (meth)acryloyl compound as essential and other polymerizable unsaturated monomers.

[0029] (Meth)acryloyl compounds include, for example, 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, "isostearyl acrylate" (manufactured by Osaka Organic Chemical Industry Co., Ltd., ISTA highly branched long-chain alkyl acrylate), etc.; alicyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, etc.; aralkyl (meth)acrylates such as benzyl (meth)acrylate, etc.; alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, etc.; fluoroalkyl (meth)acrylates such as hexafluoroisopropyl (meth)acrylate, perfluorooctylmethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, etc.; phosphate group-containing (meth)acrylates such as (2-(meth)acryloyloxyethyl) acid phosphate, (2-(meth)acryloyloxypropyl) acid phosphate, etc.; 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, diacetone (meth)acrylamide, etc.; 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, 3,4-epoxycyclohexylpropyl (meth)acrylate, etc.; 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, and dicyclopentenyl (meth)acrylate; 1,2,2,6,6-pentamethylpiperidyl (meth)acrylate, 2,2,6,6-tetramethylpiperidinyl (meth)acrylate, etc.; 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 and other quaternary ammonium base-containing (meth)acrylates; (meth)acrylates having a polyoxyalkylene chain with an alkoxy group at the molecular end, etc. These can be used alone or in combination of two or more thereof.

[0030] In addition, examples of other polymerizable unsaturated monomers include (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 (e.g., 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; polymerizable unsaturated monomers containing an oxidation-curing group such as a reaction product of an epoxy group-containing polymerizable unsaturated monomer or a hydroxyl group-containing polymerizable unsaturated monomer and an unsaturated fatty acid; fluorovinyl ethers such as fluoroalkyl trifluorovinyl ether and perfluoroalkyl trifluorovinyl ether. These can be used alone or in combination of two or more thereof.

[0031] 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.

[0032] In this specification, "(meth)acrylate" means 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.

[0033] 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.

[0034] Iron supply material chelated with humic acid In the present invention, the iron supply material chelated with humic acid can be prepared by mixing humic acid and the iron supply material.

[0035] Examples of the humic acid include fulvic acid, humic acid, etc., and fulvic acid is preferred. In the present specification, the fulvic acid refers to a component that constitutes humus and is soluble in both alkali and acid. The molecular weight of the fulvic acid is not limited, and examples thereof include those having a weight average molecular weight of less than 10,000 (for example, 7,000 or less, 5,000 or less, 3,000 or less, etc.). In the present specification, the humic acid refers to a component that constitutes humus and is soluble in alkali but insoluble in acid. The molecular weight of the humic acid is not limited, and examples thereof include those having a weight average molecular weight of 10,000 or more and less than 100,000 (for example, 70,000 or less, 50,000 or less, 30,000 or less, etc.). Here, the humus refers to a product obtained by decomposition of dead plants and animal carcasses in soil by microorganisms. Humus usually contains various organic compounds. These humic acids can be used alone or in combination of two or more.

[0036] Examples of the iron supply material include polysilicate iron liquid (PSI), metal particles such as steel chips, iron powder, iron oxide, etc., and polysilicate iron liquid (PSI) etc. are preferred. These iron supply materials can be used alone or in combination of two or more.

[0037] The mixing ratio of the iron supply material and the humic acid is not limited, but it is preferable to mix the iron supply material and the humic acid so that the humic acid is 30 to 90 parts by mass, preferably 45 to 75 parts by mass, per 1 part by mass of the iron component contained in the iron supply material. In the present specification, the content of the "iron component" means the total content of iron and iron ions released from iron compounds (such as iron oxide) contained in the iron supply material.

[0038] In the preparation of the iron supply material chelated with humic acid, it is preferable to age the mixture after mixing the humic acid and the iron supply material. In the present invention, examples of the iron supply material chelated with humic acid include iron silicate fulvate material, iron fulvate material, iron silicate humate material, iron humate material, etc., and iron silicate fulvate material is preferred.

[0039] In the present invention, the d50 (volume average particle diameter) of the iron supply material chelated with the humic acid is not limited. 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 Co., Ltd.).

[0040] Hereinafter, as a non-limiting preferred example of the iron supply material chelated with the humic acid, an iron fulvate silica material will be described, but the present invention is not limited to such an embodiment.

[0041] Ferric fulvate silica material In the present invention, the iron fulvate silica material can be produced, for example, by 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 is produced by fermentation and sterilization treatment of sewage sludge and wood chips, and aging. The production of the iron fulvate silica can be carried out according to the method described in Patent Document 2. Specifically, for example, it is as follows.

[0042] In the present invention, as the object to which the polysilicate iron liquid agent (PSI) is added, a fermentation product obtained by fermentation and sterilization treatment of sewage sludge and wood chips can be used. For example, in the fermentation step in the preparation of the above fermentation product, harmful microorganisms can be killed or inactivated by adjusting the fermentation temperature and time.

[0043] Commercially available polysilicate iron solution (PSI) can be used as appropriate. By using polysilicate iron solution (PSI) mainly composed of iron and silica, it is preferable because it can supply soluble silica and iron and easily elute soluble silica and iron fulvate into water and soil.

[0044] The addition amount of polysilicate iron solution (PSI) to the above fermentation product is 50 mg / kg to 7000 mg / kg, preferably 500 mg / kg to 5000 mg / kg, per kg of the mass of the fermentation product. From the viewpoint of suppressing the adhesion of marine fouling organisms, the above range is preferable. Also, in terms of silica iron conversion (FeCl 3 +Na 2 O·nSiO 2 ·xH 2 O) in the polysilicate iron solution (PSI), it is preferable to add PSI so that it is preferably 3.5 mg / kg to 2030 mg silica iron / kg fermentation product, more preferably 7 mg / kg to 1450 mg silica iron / kg fermentation product, per kg of the mass of the fermentation product.

[0045] In the present invention, the d50 (volume average particle diameter) of the iron fulvate silica material is not limited, for example, it is 0.01 to 300 μm, preferably 0.1 to 200 μm, more preferably 1 to 50 μm. From the viewpoints of crack resistance and water adhesion resistance, the above range is preferable.

[0046] The content ratio of the iron component and silica in the iron fulvate silica material is not limited. For example, the latter is 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, with respect to 1 part by mass of the former. 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 iron fulvate silica material. Also, the content ratio of the iron component and fulvic acid in the iron fulvate silica material is not limited. For example, the latter is 30 to 90 parts by mass, preferably 45 to 75 parts by mass, with respect to 1 part by mass of the former.

[0047] The anti - adhesion 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 iron supply material chelated with humic acid, or a material containing soluble silica as the iron supply material (for example, fulvic acid iron silica material) may be used to prepare the composition. When using soluble silica, its content is not limited. As the ratio of the iron component derived from the iron supply material to silica, for example, when the former is 1 part by mass, the latter is 0.5 - 10 parts by mass, preferably 1 - 5 parts by mass.

[0048] 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, which is the resin component described in the section of "at least one resin component" unless otherwise specified) and the iron supply material chelated with the humic acid (for example, fulvic acid iron silica material).

[0049] In the present invention, the blending ratio of the resin component and the iron supply material chelated with the humic acid is not limited. For example, when the former is 1 part by mass, the latter can be used in the range of 0.01 - 10 parts by mass, preferably 0.1 - 8 parts by mass, more preferably 1 - 6 parts by mass. From the perspective of crack resistance, it is preferable that the blending ratio of the resin component and the iron supply material chelated with the humic acid is within the above range.

[0050] The mixing of the resin component and the iron supply material chelated with humic acid can be carried out by using a method known per se. For example, a disper, shaker, bead mill, ball mill, pebble ball mill, homogenizer, ultrasonic disperser, kneader, extruder, planetary mixer, etc. can be used. The temperature during mixing is not particularly limited and can be set, for example, in the range of 0 - 60°C, preferably 20 - 40°C. The mixing time is also not limited and can be set, for example, in the range of 0.05 - 5 hours, preferably 0.1 - 2 hours.

[0051] In the step of mixing the resin component in the present invention with the iron supply material chelated with humic acid, the resin component may be used in a state of being mixed with other raw materials. Also, the iron supply material chelated with humic acid 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 with an iron supply material chelated with humic acid" is not limited as long as the resin component and the iron supply material chelated with humic acid are mixed, and it may be any of mixing only the resin component with only the iron supply material chelated with humic acid; mixing a mixture containing the resin component and other raw materials with the iron supply material chelated with humic acid; mixing the resin component with a mixture containing the iron supply material chelated with humic acid and other raw materials; and mixing a mixture containing the resin component and other raw materials with a mixture containing the iron supply material chelated with humic acid and other raw materials.

[0052] Examples of the raw materials other than the resin component and the iron supply material chelated with humic acid include plasticizers and the like. Examples of plasticizers include phosphate esters (such as tricresyl phosphate), chlorinated paraffins (such as chlorinated normal paraffin), liquid paraffin, n-paraffin, phthalic acid esters (such as isodecyl phthalate), polyester resins (such as Polysizer P-29 manufactured by Dainippon Ink and Chemicals, Inc.), epoxidized oils (such as Adeka Sizer 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, its usage amount is not limited. 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.

[0053] In addition, as raw materials other than the resin component and the iron supply material chelated with humic acid, a thickener or the like may be used. Examples of the thickener 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 silica treated with micronized silica, bentonite, silica treated with a silane compound, etc., bentonite treated with a quaternary ammonium salt or the like (organic bentonite), and surface-treated calcium carbonate. These thickeners can be used alone or in combination of two or more. In addition, for the addition of the thickener, commercially available products such as DISPARLON NS-30 (containing oxidized polyethylene and fatty acid amide wax) can also be used. When using a thickener, its usage amount is not limited. For example, with respect to 1 part by mass of the resin component, the thickener component can be used in an amount of 0.001 to 0.5 part by mass, preferably 0.01 to 0.3 part by mass.

[0054] In addition, as raw materials other than the resin component and the iron supply material chelated with humic acid, 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, with respect to 1 part by mass of the resin component, the solvent can be used in an amount of 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass.

[0055] As raw materials other than the resin component and the iron supply material chelated with humic acid, for example, nutrient components and the like may be used. Examples of the above-mentioned nutrient 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 also effective as nutrient components of seaweeds. Among these substances, 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 calcium cyanamide, bone meal, oyster shell powder, etc., may also be included. More specifically, the following are mentioned. Nitrogen-containing substances (ammonium sulfate, urea, calcium cyanamide, ammonium chloride, ammonium nitrate, ammonium phosphate, metal salts of ethylenediaminetetraacetic acid (EDTA), defatted soybean powder, chicken manure, cow manure, amino acid salts, guanylurea salts, guanidine salts, oil cake, glycin, chemical fertilizers, etc.), phosphorus-containing substances (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 (potassium chloride, potassium phosphate, potassium sulfate, potassium nitrate, seaweed ash, plant ash, etc.), alkaline earth metal-containing substances (oyster shell organic lime, bone meal, fish meal, oyster shell powder, crab shell powder, calcium carbonate, etc.), etc. Regarding the nutrient components containing the above atoms in combination, they are listed representatively in the substance names containing one atom for convenience. Each of the substances exemplified above is a part of the nutrient components that can be used in the present invention. As long as it is a fertilizer substance or a nutrient component that contains the above atoms alone or in combination, even if it is other than those exemplified above, it can be used without particular limitation. These nutrient components can be used alone or in combination of two or more. Among these substances, one kind, preferably two or more kinds of nutrient components selected from nitrogen-containing substances and alkaline earth metal-containing substances are preferably used. There are no particularly strict restrictions on the combined ratio of these when using two or more nutrient components in combination. When using nutrient 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 the nutrient component 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 a nutrient component in such an embodiment.

[0056] Furthermore, in addition to the above substances, for the purpose of adjusting the 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 in the composition for preventing the adhesion of the above shellfish and crustaceans.

[0057] 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 (such as vinyl chloride, polyester, acrylic, FRP, etc.), metals (such as steel, aluminum, stainless steel, etc.), concrete, rock, wood, fiber, biodegradable fiber, and those obtained by coating a metal with a resin, etc. Resins, those obtained by coating a metal with a 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, combinations thereof, etc. The method of 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 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, 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, which contains the composition of the present invention. In this embodiment, examples of the film of the present invention include a composition containing the at least one resin component and an iron supply material chelated with humic acid, and those in a dried and / or cured state, etc.

[0058] Also, in one embodiment, by producing a resin molded body using the composition of the present invention itself, 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, which contains the composition of the present invention. 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 of the present invention.

Examples

[0059] Hereinafter, the present invention will be described in more detail by way of examples, but it is not limited thereto.

[0060] Comparative Example 1 Vinyl chloride-vinyl acetate copolymer resin "SOLBIN AL" manufactured by Nisshin Chemical Industry Co., Ltd. (vinyl chloride / vinyl acetate / vinyl alcohol = 92.5 / 2.5 / 5, degree of polymerization 300, molecular weight Mw = 5.3x10 4 113 g (hydroxyl value 64 mg KOH / g), 17 g of Adeka Sizer 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 mixed and dispersed at a stirring speed of about 2,000 rpm using a disper to prepare the paint composition of Comparative Example 1.

[0061] 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 at a dry film thickness of 300 μm using a bar coater, 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.

[0062] Example 1 Vinyl chloride-vinyl acetate copolymer resin "SOLBIN AL" manufactured by Nisshin Chemical Industry Co., Ltd. (vinyl chloride / vinyl acetate / vinyl alcohol = 92.5 / 2.5 / 5, degree of polymerization 300, molecular weight Mw = 5.3x10 4 113 g (hydroxyl value 64 mg KOH / g), 17 g of Adeka Sizer 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 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. (Iron Supply Material 1) Ferric fulvate material "granular ferric fulvate" manufactured by PIIAISHII BIO was prepared by the following method. After coarse pulverization in a 10 L Henschel type mixer under stirring conditions: 2000 rpm for 10 seconds, an atomizer Using the FA-SW-1 model, the main rotor inverter frequency was set at 45 Hz (= 1350 rpm), and micronization was performed in one pass. The pulverized product was sieved through a sieve with an aperture of 150 mesh using a vibrating sieve machine. The particle size distribution of the iron feedstock 1 was measured using a laser diffraction / scattering particle size distribution analyzer.

[0063] Examples 2 to 3 and Comparative Example 2 Examples 2 to 3 and Comparative Example 2 were obtained in the same manner as in Example 1, except that the formulations shown in Table 1 were used. The iron feedstocks 2 (D50 20 μm) and 3 were prepared as follows. Further, a coating film on a rigid PVC plate was formed 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 produced. (Iron feedstock 2 (D50 20 μm)) Iron feedstock 2 (D50 20 μm) was obtained in the same manner as iron feedstock 1, except that the iron fulvate silica material "Ryugu no Tsukai" manufactured by Koyo Co., Ltd. was used instead of the iron fulvate material "Granular Ferrous Humate" manufactured by Piiai Shii 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 Chemical Industry Co., Ltd.) onto 10 tons of a fermented 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 (FeCl 3 ) 5 - 27 wt / wt% Sodium silicate (Na 2 O·nSiO 2 ·xH 2 O (n = approximately 3) 2 wt / wt% (as SiO 2 ) Sulfuric acid 1 wt / wt% Water 70 - 92 wt / wt%.

[0064] The analytical values of the active ingredients in the obtained "Ryugu no Tsukai" are as follows. Humic acid 2,400 mg / L Soluble iron 39 mg / L Soluble silica 105 mg / L The above analytical values are the analytical values of the filtrate obtained by filtering the "Messenger of Ryugu" (50 g) stored at room temperature in 100 ml of deionized water for 20 days through a 5A filter paper. Fulvic acid and soluble iron were analyzed by the Japan Food Function Analysis Laboratory Co., Ltd. Available silica was analyzed using an ICP-MS analyzer at the Kurume Research Park Co., Ltd.

[0065] The obtained "Messenger of Ryugu" was roughly pulverized with a 10 L Henschel mixer under stirring conditions of 2000 rpm for 10 seconds, and then finely pulverized by passing it once through an atomizer FA-SW-1 type with the main rotor inverter frequency set at 45 Hz (= 1350 rpm). This pulverized product was sieved with a sieve having an aperture of 150 mesh using a vibrating sieve machine to obtain an iron feed material 2 (D50 20 μm). The particle size distribution of the obtained iron feed material 2 (D50 20 μm) was measured with a laser diffraction / scattering particle size distribution measuring device. (Iron feed material 3) An iron feed material 3 was obtained in the same manner as for iron feed material 1, except that the fulvic acid iron silica material "Chelate Marine K1 type" manufactured by Nichi-Nichi Sangyo Co., Ltd. was used instead of the fulvic acid iron material "Granular Fulvo Iron" manufactured by Piyoshi Bio Co., Ltd. "Chelate Marine K1 type" contains silicon, but it is not obtained by a method including a step of mixing a liquid substance composed of silica iron in the range of 50 mg to 7000 mg with 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.

[0066]

Table 1

[0067] In the above table, the examples and comparative examples in which the column of "base material" is described as "-" indicate that resin molded bodies were produced with each composition.

[0068] Example 4 113 g of acrylic resin PARALOID B-44 Resin (solid content 100%) manufactured by DOW Co., Ltd., and 17 g of ADEKA SAIZER O-130P manufactured by ADEKA Co., Ltd. were 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, 402 g of iron supply material 2 (D50 20 μm) shown below was mixed and dispersed at a stirring speed of about 2,000 rpm using a disper to prepare the coating composition of Example 4. 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 produce a test plate for marine evaluation.

[0069] Example 5 141 g of polyester polyol resin XR-1016 (solid content 80%, hydroxyl value 70 mg KOH / g) manufactured by ToShin YuShi Co., Ltd., and 17 g of ADEKA SAIZER O-130P manufactured by ADEKA Co., Ltd. were 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, 402 g of iron supply material 2 (D50 20 μm) shown below was mixed and dispersed at a stirring speed of about 2,000 rpm using a disper to prepare the coating composition of Example 5. 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 produce a test plate for marine evaluation.

[0070] Example 6 Except for using the formulation shown in Table 1, in the same manner as in Example 1, the coating composition of Example 6 was obtained. 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 produce a test plate for marine evaluation.

[0071] Example 7 Except for using the composition described in Table 1, a coating composition was obtained in the same manner as in Example 1. A polyethylene terephthalate net as a substrate was prepared. The obtained coating composition was immersed in the net, and after lifting the net from the coating, the excess coating was removed, air-dried, and then fixed to an iron frame of 35 cm × 45 cm.

[0072] Example 8 70 g of polypropylene resin with an MFR (at a temperature of 230 °C and a load of 2.16 kg) of 45 g / 10 min and 30 g of iron feedstock 2 (D50 20 μm) were mixed. The resulting mixture was melt-kneaded using a twin-screw kneading extruder, and after the melt-kneaded material was extruded into strands, it was cut to produce resin pellets. The resin pellets were injection-molded using an injection molding machine to produce a sheet with 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.

[0073] Example 9 A paint composition of Example 9 was obtained in the same manner as in Example 1, except that the formulation in Table 1 was used. Iron feedstock 2 (D50 150 μm) was prepared as follows. Except for using the paint composition obtained above, 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. (Iron feedstock 2 (D50 150 μm)) Iron feedstock 2 (D50 150 μm) was obtained in the same manner as iron feedstock 2 (D50 20 μm), except that the inverter frequency setting and the mesh opening of the mesh sieve were as follows. The "messenger of Ryugu" was coarsely pulverized with a 10 L Henschel mixer under stirring conditions of 2000 rpm for 10 seconds, and then finely pulverized by passing it once through an atomizer FA-SW-1 type with a main rotor inverter frequency setting of 35 Hz (= 1050 rpm). This pulverized product was sieved with a sieve having a mesh opening of 50 meshes using a vibrating sieve machine to obtain iron feedstock 2 (D50 150 μm). The particle size distribution of the obtained iron feedstock 2 (D50 150 μm) was measured with a laser diffraction / scattering particle size distribution measuring device.

[0074] Example 10 A paint composition of Example 10 was obtained in the same manner as in Example 1, except that the formulation in Table 1 was used. The obtained paint composition was applied to a concrete block with a width of 20 cm, a depth of 10 cm, and a height of 6 cm with 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 produced.

[0075] Examples 11 to 13 Except for using the formulations shown in Table 1, coating compositions of Examples 11 to 13 were obtained in the same manner as in Example 1. Except for using the coating compositions obtained above, a coating film on a rigid PVC plate was formed in the same manner as in Comparative Example 1, and a test panel for marine evaluation was produced.

[0076] Comparative Example 3 Only a resin not containing iron feedstocks 1 to 3, specifically using the composition described in Table 1, a sheet was produced in the same manner as in Example 8 above and used as a test panel for marine evaluation in Comparative Example.

[0077] Marine evaluation test The test panels for marine evaluation thus produced were fixedly installed using piles in the tidal flat 100 m off the coast of Nagashima, Tamana District, Kumamoto Prefecture. The average tide level of this test site is about 3 - 4 m, and the maximum tide level is 5 - 6 m. Three months after installation, a crack resistance test and an antifouling performance test were conducted. · Crack resistance test: Using a test piece, the coating film was visually observed to check for the presence or absence of cracks. S: No cracks were observed. A: Fine cracks were observed in a partial range of the coating film surface. B: Fine or distinct cracks were observed in a wide range of the coating film surface. C: Cracks reaching the substrate were observed. Grade B or above is considered qualified, grade A is more preferable than grade B, and grade S is the most preferable. · Antifouling performance test A: On the coating film surface after being immersed in the sea, the area where attached aquatic organisms such as shellfish and crustaceans are attached is less than 30% of the surface before being immersed in seawater. B: On the coating film surface after being immersed in the sea, the area where attached aquatic organisms such as shellfish and crustaceans are attached is 30% or more and less than 70% of the coating film surface before being immersed in seawater. C: On the coating film surface after being immersed in the sea, the area where attached aquatic organisms such as shellfish and crustaceans are attached is 70% or more of the coating film surface before being immersed in seawater. Grade B or above is considered qualified, and grade A is more preferable than grade B.

[0078] Water resistance adhesion test The coating compositions of Examples 1 to 6, 9 to 13, and Comparative Examples 1 and 2 were each applied to each substrate described in Table 1 with an applicator so that the dry film thickness became 200 μm. Then, they were dried at room temperature for 24 hours and further dried at 70 °C for 1 hour to obtain test panels for water resistance adhesion. After each of the obtained test panels for water resistance adhesion was immersed in tap water at 23 °C for 12 days and then pulled out, it was dried at room temperature for 6 hours. 100 grids of 2 mm × 2 mm were made in accordance with JIS K 5600-5-6 (1990). An adhesive tape was attached to the surface, and after it was rapidly peeled off, the remaining state of the grid coating film was examined, and the water resistance adhesion was evaluated according to the following criteria. Evaluation was not performed for Example 7 in which grids could not be made, and Examples 8 and Comparative Example 3 in which there was no coating film. S, A, and B are passing grades, A is more preferable than B, and S is the most preferable. The evaluation results are also shown in Table 1. S: 100 grid coating films remain, and there is no edge peeling. A: 100 grid coating films remain, and there is edge peeling. B: The number of remaining grid coating films is 99 or less, and it is partially adhered. C: The entire surface is peeled off.

Claims

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

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

3. 3. The composition for preventing adhesion of shellfish and crustaceans according to claim 2, further comprising soluble silica.

4. A composition for preventing adhesion of shellfish and crustaceans as described in claim 3, wherein the humic acid chelated iron source and / or soluble silica has a d50 (volume average particle size) in the range of 0.01 to 300 μm.

5. A coating composition for preventing adhesion of shellfish and crustaceans, comprising the composition according to any one of claims 1 to 4.

6. A film for preventing adhesion of shellfish and crustaceans, comprising the composition according to any one of claims 1 to 4.

7. A resin molded article for preventing adhesion of shellfish and crustaceans, comprising the composition according to any one of claims 1 to 4.

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