Algae-preventing agent, algae-preventing coating composition, laminate, building, algae-preventing resin composition, and molded article

Abstract

Provided is an algaecide which has high compatibility with a resin and high algaecide resistance, and which has reduced influence on the appearance of an object to be applied. This algicide for preventing the adhesion of terrestrial algae contains a fatty acid having 1-22 carbon atoms and a fatty acid metal salt of a metal, wherein the metal is copper, bismuth, zinc, magnesium, cobalt or a rare earth element.

Description

Technical Field

[0001] The present invention relates to an algaecide, an algaecide coating composition, a laminate, a building, an algaecide resin composition, and a molded body. Background Art

[0002] Not only bacteria and viruses float in the air, but also terrestrial algae. These algae attach and grow in areas of buildings with high humidity (such as exterior and interior walls, water towers, and other equipment), causing foul odors and damaging the aesthetics of the buildings themselves.

[0003] In recent years, regardless of the purpose of a building, such as a residence or office, there has been a growing demand for maintaining the aesthetics of the building in order to attract and retain occupants. Algae-resistant coatings have been proposed to address this need (e.g., Patent Documents 1-2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2011-079816

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2005-272320 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] The anti-algae agents described in the patent documents are likely to precipitate when mixed with a binder resin. This leads to a problem in that the anti-algae agents themselves precipitate when applied to the surface of a substrate, thereby impairing the appearance.

[0010] The problem to be solved by the present invention is to provide an anti-algae agent having high compatibility with resins and high anti-algae properties and having reduced influence on the appearance of the object to which it is applied.

[0011] Another problem to be solved by the present invention is to provide an anti-algae coating composition that can provide an anti-algae coating without impairing the surface appearance and surface feel.

[0012] Another problem to be solved by the present invention is to provide a laminate and a molded article that can exhibit anti-algae properties without impairing the surface appearance and surface feel.

[0013] Means for solving problems

[0014] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that an algaecide containing a specific fatty acid metal salt exhibits high algaecide properties while ensuring high compatibility with resins, thereby completing the present invention.

[0015] That is, the present invention relates to the following anti-algae agents and the like.

[0016] 1. An algaecide for preventing the attachment of terrestrial algae, comprising a fatty acid metal salt of a fatty acid having 1 to 22 carbon atoms and a metal, wherein the metal is copper, bismuth, zinc, magnesium, cobalt or a rare earth element.

[0017] 2. The algaecide according to item 1, wherein the fatty acid is 2-ethylhexanoic acid, neodecanoic acid, isononanoic acid, cyclohexaneic acid, lauric acid, stearic acid, isostearic acid or palmitic acid.

[0018] 3. The algaecide according to 1 or 2, wherein the metal is bismuth or a rare earth element.

[0019] 4. An anti-algae coating composition comprising the anti-algae agent according to any one of 1 to 3 and a binder resin.

[0020] 5. The anti-algae coating composition according to 4, wherein the binder resin is one or more selected from acrylic resins, vinyl acetate resins, styrene resins, vinyl chloride resins, olefin resins, urethane resins, urea-formaldehyde resins, urethane urea-formaldehyde resins, epoxy resins, melamine resins, phenolic resins, polyester resins, alkyd resins, silicone resins, acrylonitrile / styrene copolymer resins, and acrylonitrile / butadiene copolymer resins.

[0021] 6. The anti-algae coating composition according to 4 or 5, further comprising 0.01 to 30 parts by mass of the metal derived from the anti-algae agent based on 100 parts by mass of the resin solid content.

[0022] 7. A laminate comprising a coating layer of the anti-algae coating composition according to any one of 4 to 6 and a substrate.

[0023] 8. A building comprising a coating layer of the anti-algae coating composition according to any one of 4 to 6 on its outer wall and / or inner wall.

[0024] 9. An anti-algae resin composition comprising the anti-algae agent according to any one of 1 to 3 and a resin.

[0025] 10. A molded article obtained by molding the anti-algae resin composition according to 9.

[0026] Effects of the Invention

[0027] The present invention can provide an anti-algae agent having high compatibility with resins and high anti-algae properties, and having reduced influence on the appearance of the application object.

[0028] The present invention can provide an anti-algae coating composition that can perform anti-algae coating without impairing the surface appearance and surface feel.

[0029] The present invention can provide a laminate and a molded article that can exhibit anti-algae properties without impairing the surface appearance and surface feel. DETAILED DESCRIPTION

[0030] Hereinafter, one embodiment of the present invention will be described. The present invention is not limited to the following embodiment, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.

[0031] It should be noted that the compounds in this specification may be derived from fossil resources or biological resources.

[0032] [Algaecide]

[0033] The algaecide of the present invention can prevent the attachment of terrestrial algae to the area where it is applied. Terrestrial algae thrive in moist or water-connected environments. However, because the algaecide of the present invention contains a fatty acid metal salt, which has a high water resistance, it can exhibit its algaecide effect for a long time. Furthermore, the fatty acid metal salt has a high compatibility with the binder resin and does not precipitate from the algaecide coating (described later) and deteriorate its appearance.

[0034] The term "terrestrial algae" as used herein refers to algae that can grow on land and do not conform to the definition of general terrestrial plants such as seed plants, ferns, and mosses.

[0035] Specific examples of terrestrial algae include cyanobacteria such as the genera Oscillatoria and Phormidium; and green algae such as the genera Chlamydomonas, Chlorococcum, Chlorella, Desmodesmus, Klebsormidium, Trebouxiophyceae, and Ulothrix.

[0036] Hereinafter, the anti-algae agent of the present invention will be described.

[0037] (Fatty acid metal salt)

[0038] The algaecide of the present invention contains fatty acid metal salt of fatty acid having 1 to 22 carbon atoms and metal, wherein the metal is copper, bismuth, zinc, magnesium, cobalt or rare earth element.

[0039] Hereinafter, the fatty acid metal salt may be referred to as "the fatty acid metal salt of the present invention."

[0040] The fatty acid metal salt of the present invention is a compound represented by the following general formula (1).

[0041] [Chemistry 1]

[0042]

[0043] (In the above general formula (1),

[0044] R 1 is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms,

[0045] n1 is an integer ranging from 1 to 4,

[0046] M 1 is copper, bismuth, zinc, magnesium, cobalt or a rare earth element.)

[0047] In the above general formula (1), when n1 is an integer greater than or equal to 2, a plurality of R 1 They can be the same as each other or different.

[0048] R 1 The alkyl group having 1 to 21 carbon atoms may be a linear alkyl group or a branched alkyl group, or may contain an alicyclic structure.

[0049] R 1 The hydrogen atom or the alkyl group with 1 to 21 carbon atoms corresponds to the group consisting of R used in the manufacture of the fatty acid metal salt. 1 A carboxylic acid residue obtained by removing a carboxyl group (COOH) from a carboxylic acid having 1 to 22 carbon atoms, represented by COOH. Examples of such carboxylic acid residues include formic acid residues, acetic acid residues, propionic acid residues, butyric acid residues, valeric acid residues, hexanoic acid residues, 2-ethylbutyric acid residues, heptanoic acid residues, octanoic acid residues, acrylic acid residues, methacrylic acid residues, octylic acid residues (2-ethylhexanoic acid residues), neodecanoic acid residues, cyclohexaneic acid residues, isononanoic acid residues, eleostearic acid residues, tall oil fatty acid residues, coconut oil fatty acid residues, soybean oil fatty acid residues, linseed oil fatty acid residues, safflower seed oil fatty acid residues, dehydrated castor oil fatty acid residues, tung oil fatty acid residues, lauric acid residues, myristic acid residues, palmitic acid residues, stearic acid residues, isostearic acid residues, and oleic acid residues.

[0050] About R 1 The alkyl group having 1 to 21 carbon atoms is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 7 to 11 carbon atoms, from the viewpoint of adhesion to a substrate described later.

[0051] R 1Preferred are 2-ethylhexanoic acid residues, neodecanoic acid residues, isononanoic acid residues, cycloalkanoic acid residues, lauric acid residues, stearic acid residues, isostearic acid residues, or palmitic acid residues. From the viewpoint of transparency, 2-ethylhexanoic acid residues, neodecanoic acid residues, isononanoic acid residues, cycloalkanoic acid residues, or isostearic acid residues are more preferred.

[0052] M 1 The rare earth elements refer to one or more selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).

[0053] M 1 Preferably, it is bismuth or a rare earth element, more preferably bismuth, lanthanum or neodymium. 1 In the case of these metals, the anti-algae agent can suppress coloration derived from the metal and ensure high transparency.

[0054] n1 is the number of cells that are connected by M 1 The value determined by the ionic valence of the metal atom, for example, if M 1 If it is bismuth, then n1 is 3. If M 1 If it is neodymium, n1 is 3.

[0055] The fatty acid metal salt contained in the algaecide of the present invention may be a single type or may be two or more types of fatty acid metal salts having different structures.

[0056] The algaecide of the present invention only needs to contain the fatty acid metal salt of the present invention. For example, it can consist essentially of the fatty acid metal salt of the present invention. Here, "consisting essentially of" means that the fatty acid metal salt content is 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the total amount of the algaecide of the present invention.

[0057] The fatty acid metal salt of the present invention can be produced by a known method, or a commercially available product can be used.

[0058] (Metal Complex)

[0059] The fatty acid metal salt of the present invention may be in the form of a metal complex coordinated with a heteroatom-containing ligand.

[0060] The heteroatom-containing ligand forming the metal complex may be any ligand having one or more heteroatoms selected from nitrogen, oxygen, sulfur, and phosphorus in the molecule. Examples of the heteroatom-containing ligand include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), 4-dimethylaminoamine (DMAP), dicyandiamide (DICY), tri-n-butylamine, dimethylbenzylamine, butylamine, 1,2-propylenediamine, 1,2-cyclohexanediamine, and octylamine. , monoethanolamine, diethanolamine, triethanolamine, 2-[[(2-dimethylamino)ethyl]methylamino]ethanol, picolinic acid, 2,2'-[propane-1,2-diylbis(nitromethine)]diphenol (Japanese: 2,2'-[プロパン-1,2-ジイルビス(アザニリリリデンメタニリリリデン)]ジフェノール), imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-amino propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, 8-quinolinol, 5-chloro-8-quinolinol, 2,2'-bipyridine and its derivatives, 2,2'-[propane-1,2-diylbis(nitromethyl)]diphenol and its derivatives, 2,2'-methylenebis[6 -(2H-benzotriazol-2-yl)-4-tert-octylphenol); amine compounds such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; sulfur compounds such as thiolactic acid, 2-aminothiophenol, and 2,2'-dithiodiphenylamine.

[0061] The heteroatom-containing ligand is preferably one or more amine ligands selected from picolinic acid, 2-{[(2-dimethylamino)ethyl]methylamino}ethanol, 1,2-propylenediamine, 1,2-cyclohexanediamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 8-quinolinol, 5-chloro-8-quinolinol, 2,2'-bipyridine and its derivatives, and 2,2'-[propane-1,2-diylbis(nitromethine)]diphenol and its derivatives.

[0062] The heteroatom-containing ligand forming the metal complex may be a single type or two or more types having different structures may be used.

[0063] In the metal complex, the ratio (molar ratio) of the fatty acid metal salt to the heteroatom-containing ligand is, for example, in the range of 0.1 to 12 mol, preferably 0.3 to 10 mol, and more preferably 0.5 to 10 mol of the heteroatom-containing ligand per 1 mol of the metal atom in the fatty acid metal salt.

[0064] The metal complex of a fatty acid metal salt and a heteroatom-containing ligand can be produced by a known method, such as by reacting a fatty acid metal salt with a heteroatom-containing ligand.

[0065] [Coating composition]

[0066] The coating composition of the present invention contains the antialgae agent of the present invention and a binder resin.

[0067] Since the algaecide of the present invention has high compatibility with the binder resin, a coating obtained from a coating composition containing the algaecide of the present invention can exhibit algaecide properties while reducing the effects on appearance such as loss of transparency.

[0068] The content of the anti-algae agent of the present invention in the coating composition of the present invention is not particularly limited. For example, the amount of metal derived from the anti-algae agent may be in the range of 0.01 to 30 parts by mass relative to 100 parts by mass of the resin solids, preferably in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the resin solids, more preferably in the range of 0.05 to 10 parts by mass relative to 100 parts by mass of the resin solids, and even more preferably in the range of 0.1 to 9 parts by mass relative to 100 parts by mass of the resin solids.

[0069] The "resin solid content" herein refers to the total amount of solid components such as the binder resin contained in the coating composition except the solvent.

[0070] The curing properties of the binder resin contained in the coating composition of the present invention are not particularly limited. For example, when the binder resin is an acrylic resin, the acrylic resin may be a thermosetting acrylic resin or an active energy ray-curable acrylic resin.

[0071] Furthermore, the form of the binder resin is not particularly limited and may be an emulsion resin or a latex resin.

[0072] The binder resin may be either a water-based resin or a water-insoluble resin (solvent-based resin).

[0073] In this application, the term "water-soluble resin" means that the amount of water required to dissolve 1 g of the resin at 20° C. is less than 10 ml. The term "water-insoluble resin" means a resin other than the aforementioned "water-soluble resin."

[0074] Specific examples of the binder resin include acrylic resins, vinyl acetate resins, styrene resins, vinyl chloride resins, olefin resins, urethane resins, urea resins, urethane urea resins, acrylic urethane resins, epoxy resins, melamine resins, phenolic resins, polyester resins, alkyd resins, silicone resins, polyphenylene sulfide resins, acrylonitrile / styrene copolymer resins, acrylonitrile / butadiene copolymer resins, and acrylonitrile / butadiene / styrene copolymer (ABS) resins.

[0075] The binder resin also includes resins obtained by modifying the above resins. For example, if it is a phenolic resin, it also includes a rosin-modified phenolic resin.

[0076] The binder resin contained in the coating composition of the present invention may be a single type or two or more types.

[0077] The content of the binder resin in the coating composition of the present invention is not particularly limited and can be appropriately set within the range of, for example, 10 to 100% by mass relative to the total mass of the resin solid content of the coating composition.

[0078] The coating composition of the present invention only needs to contain the anti-algae agent of the present invention and a binder resin, and may further contain a dispersion medium. The dispersion medium is a substance added for the purpose of adjusting the viscosity of the coating composition, and may be either an aqueous medium or an oily medium.

[0079] Specific examples of the dispersion medium include water, monofunctional alcohols such as 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methyl ethyl ketone, methanol, ethanol, n-propanol, and isopropanol, various glycols, polyols such as glycerol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, propylene glycol, 1,2-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2-methyl-1,3-propanediol, 1,2-hexanediol, dipropylene glycol, diethylene glycol, bisphenol A, and diols having 2 carbon atoms as bisphenol A. or 3-alkylene oxide (average addition mole number of 1 to 16) adducts, aromatic diols, alicyclic diols such as hydrogenated bisphenol A, polyoxypropylene-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane, cyclohexanediol, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, ethyl carbitol, γ-butyrolactone, various fatty acids, etc.

[0080] The dispersion medium contained in the coating composition of the present invention may be a single type or two or more types.

[0081] The content of the dispersion medium in the coating composition of the present invention is not particularly limited, and can be appropriately set so that the solid content concentration of the coating composition falls within a range of 30 to 80% by mass, for example.

[0082] The coating composition of the present invention may further contain a plasticizer.

[0083] By adding a plasticizer to the coating composition, flexibility can be imparted to the resulting coating layer and the conformability to the substrate can be improved.

[0084] The plasticizer is not particularly limited, and examples thereof include phthalates, non-aromatic dibasic acid esters, aliphatic esters, polyalkylene glycol esters, phosphate esters, trimellitic acid esters, chlorinated paraffins, hydrocarbon oils, process oils, polyethers, epoxy plasticizers, polyester plasticizers, etc., with phthalates being preferred.

[0085] Specific examples of the plasticizer include dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil, and benzyl epoxystearate.

[0086] The plasticizer contained in the coating composition of the present invention may be a single type or two or more types.

[0087] The content of the plasticizer in the coating composition of the present invention is not particularly limited, and can be appropriately set within the range of, for example, 0.1 to 50 parts by mass relative to 100 parts by mass of the resin solid content of the coating composition.

[0088] The coating composition of the present invention may contain other additives as long as it contains the anti-algae agent of the present invention, a binder resin, and optionally a dispersion medium and / or a plasticizer, and may contain other additives within a range that does not impair the effects of the present invention. Examples of such other additives include pigments, matting agents, curing agents, curing accelerators, defoaming agents, dispersants, leveling agents, thickeners, antioxidants, weathering agents, flame retardants, antistatic agents, lubricants, preservatives, and anti-algae agents other than the anti-algae agent of the present invention (e.g., isothiazolin-based compounds, thiazoline-based compounds, thiazole-based compounds, triazine-based compounds, urea-based compounds, imidazole-based compounds, benzimidazole-based compounds, pyridine-based compounds, zinc pyrithione-based compounds, and phenylphenol-based compounds).

[0089] The coating layer of the coating composition of the present invention may be a cured coating film obtained by curing the coating composition, or may be an uncured coating film of the coating composition.

[0090] When the coating layer is a cured coating film of a coating composition, the coating composition of the present invention can be applied to the substrate surface, and the resulting coating film can be cured using a curing method suitable for the binder resin (thermal curing, active energy ray curing, etc.).

[0091] As the coating composition application method, any known and commonly used coating method may be used, and examples thereof include roll coating, electrostatic coating, bar coating, gravure coating, knife coating, dip coating, and spray coating.

[0092] The substrate to be coated is not particularly limited, and examples thereof include paper, synthetic paper, steel plate, aluminum foil, glass, wood, woven fabric, knitted fabric, nonwoven fabric, gypsum board, wood board, and resin substrates.

[0093] Specific examples of the resin substrate include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film), polypropylene film (CPP: unoriented polypropylene film, OPP: biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, polycarbonate film, polyethylene terephthalate film, polymethyl methacrylate film, polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose resin film, polyvinyl alcohol film, ABS resin film, norbornene-based resin film, cyclic olefin-based resin film, polyimide resin film, polyvinyl fluoride resin film, polyvinylidene fluoride resin film, and ethylene-vinyl acetate copolymer film.

[0094] The resin substrate used may be subjected to surface treatment such as corona treatment.

[0095] When the coating composition of the present invention is applied to exterior and / or interior decoration of a building, examples of application targets include mortar substrates, concrete substrates, precast concrete panel (PC panel) substrates, and ceramic exterior wall material substrates.

[0096] In order to ensure sufficient adhesion, a sealant suitable for each of the above substrates may be applied in advance.

[0097] [Resin composition]

[0098] The resin composition of the present invention contains the anti-algae agent of the present invention and a resin.

[0099] The resin composition containing the anti-algae agent of the present invention can be used not only for coating purposes but also can be formed into a molded article exhibiting anti-algae properties by molding itself.

[0100] The resin contained in the resin composition of the present invention may be the same resin as the binder resin contained in the coating composition of the present invention.

[0101] The resin composition of the present invention may be formed by any molding method suitable for the resin used, and examples thereof include melt molding methods such as injection molding, extrusion molding, press molding (press molding), compressed air molding, and vacuum molding, and casting methods.

[0102] The coating obtained using the coating composition of the present invention and the molded article obtained using the resin composition of the present invention can be used as an anti-algae material and can be suitably used in areas with high humidity and prone to the growth of terrestrial algae. As for application purposes, they can be used in a wide range of applications, including buildings (external walls, internal walls, roofs), indoor equipment (water supply equipment switches, sinks, bathtubs, toilets, toilets, drainage components), air filters, swimming pools, sinks, flower pots, water pipes, bricks, guardrails, road signs, automobiles, sponges, sealing materials, fillings, water storage or water flow tanks or pipes, furniture, insoles, clothing, sanitary products, medical materials or instruments, bath mats, towels, bedding, etc.

[0103] Example

[0104] Hereinafter, the present invention will be described in detail using Examples and Comparative Examples.

[0105] It should be noted that the present invention is not limited to the following examples.

[0106] (Synthesis Example 1: Preparation of Lanthanum Neodecanoate)

[0107] 83.1 parts by mass of neodecanoic acid and 21.5 parts by mass of lanthanum oxide were reacted at 130° C., dehydrated under reduced pressure at 130° C., and then 107.6 parts by mass of cyclohexane was added to obtain 208.5 parts by mass of a lanthanum neodecanoate solution. The lanthanum content of the obtained lanthanum neodecanoate was 8.8% by mass.

[0108] (Synthesis Example 2: Preparation of Copper Neodecanoate)

[0109] 217.1 parts by mass of neodecanoic acid and 36.0 parts by mass of sodium hydroxide were reacted at 80°C, and 100.0 parts by mass of copper sulfate was further added and reacted at 80°C. The by-produced sodium sulfate was washed with water, and then dehydrated under reduced pressure at 130°C. 76.2 parts by mass of petroleum hydrocarbons were added to obtain 301.6 parts by mass of a copper neodecanoate solution. The copper content of the resulting copper neodecanoate was 8% by mass.

[0110] (Synthesis Example 3: Preparation of Bismuth Octanoate)

[0111] 330.6 parts by mass of octanoic acid and 125.0 parts by mass of bismuth oxide were reacted at 130° C. and dehydrated under reduced pressure at 130° C. to obtain 439.5 parts by mass of a bismuth octanoate (bismuth 2-ethylhexanoate) solution. The bismuth content of the obtained bismuth octanoate was 25% by mass.

[0112] (Synthesis Example 4: Preparation of Zinc Octoate)

[0113] 277.0 parts by mass of octanoic acid, 100.0 parts by mass of zinc oxide, and 5.0 parts by mass of water were reacted at 120° C., and dehydrated under reduced pressure at 120° C. to obtain 360 parts by mass of a zinc octanoate solution. The zinc content of the obtained zinc octanoate was 22% by mass.

[0114] (Synthesis Example 5: Preparation of Magnesium Caprylate)

[0115] 461.4 parts by mass of octanoic acid were reacted with 71.9 parts by mass of magnesium hydroxide and 411.4 parts by mass of petroleum hydrocarbons at 110°C. After dehydration at 90°C under reduced pressure, 35.9 parts by mass of diethylene glycol butyl ether was added to obtain 1000 parts by mass of a magnesium octanoate solution. The magnesium content of the resulting magnesium octanoate was 3.0% by mass.

[0116] (Synthesis Example 6: Preparation of cobalt octanoate)

[0117] 319.0 parts by mass of octylic acid and 100.0 parts by mass of cobalt hydroxide were reacted at 130° C., dehydrated under reduced pressure at 130° C., and then 134.2 parts by mass of petroleum hydrocarbons were added to obtain 502.3 parts by mass of a cobalt octylate solution. The cobalt content of the obtained cobalt octylate was 12% by mass.

[0118] (Synthesis Example 7: Preparation of Neodymium Neodecanoate)

[0119] 224.8 parts by mass of neodecanoic acid and 60.0 parts by mass of neodymium oxide were reacted at 130°C, dehydrated under reduced pressure at 130°C, and then 306.9 parts by mass of cyclohexane was added to obtain 570.0 parts by mass of a neodymium neodecanoate solution. The neodymium content of the obtained neodymium neodecanoate was 8.8% by mass.

[0120] (Examples 1-12 and Comparative Example 1: Preparation of Urethane Resin-Coated Substrates and Open System Algae-Resistant Test)

[0121] The anti-algae agents shown in Tables 1 and 2 were added to a urethane resin ("BURNOCK 16-416" manufactured by DIC Corporation) in the amounts shown in Tables 1 and 2 to prepare coating compositions.

[0122] The prepared coating composition was applied to a PET film (thickness: 188 μm) using a coater to a wet film thickness of 152 μm. The resulting coated substrate was dried at room temperature for one week and then cut into 5 cm x 5 cm pieces. This method produced an anti-algae agent sample consisting of a laminate of a urethane resin coating and a PET substrate.

[0123] In all the anti-algae agent samples of Examples 1 to 12, no precipitation of the fatty acid metal salt in the coating layer was visually confirmed, and the urethane resin coating layer had high transparency.

[0124] In 10 liters of tap water, 11 g of OAT house No. 1, 7.5 g of OAT house No. 2, and 0.5 g of OAT house No. 5 manufactured by OAT Agrio were dissolved as fertilizers to prepare a culture solution.

[0125] 65 mL of the above-mentioned culture solution was weighed and placed in a transparent plastic frustum-shaped side dish cup (66 mm × 66 mm × 28 mm). The sample prepared above was floated on the surface of the culture solution in this cup, with the coating facing the surface. The cup was then placed in a sunny window. The cup with the sample floating on it was left untouched for one month. The algae growth in the culture solution was visually observed after one month, and the anti-algae properties in the open system were evaluated according to the following criteria. The results are shown in Tables 1 and 2.

[0126] 0: no algae production;

[0127] 1: Sporadic occurrence of algae.

[0128] 2: Algae production was faintly confirmed throughout the culture medium;

[0129] 3: The production of algae was clearly confirmed throughout the culture medium;

[0130] 4: Production of algae was observed at a high concentration throughout the entire culture solution, but a portion of the cup bottom could not be visually observed.

[0131] [Table 1]

[0132]

[0133] [Table 2]

[0134]

[0135] The metal contents in Tables 1 and 2 are the metal contents derived from the fatty acid metal salts. For example, in Example 1, the coating composition contained 0.88 parts by mass of lanthanum derived from lanthanum neodecanoate per 100 parts by mass of the resin solids (urethane resin).

[0136] From the results in Tables 1 and 2, it can be confirmed that the fatty acid metal salts prepared in the synthesis examples all exhibit anti-algae properties.

[0137] (Examples 13-16 and Comparative Example 2: Preparation of Urethane Resin-Coated Substrates and Closed System Anti-algae Performance Test)

[0138] The anti-algae agents shown in Table 3 were added to a urethane resin ("BURNOCK 16-416" manufactured by DIC Corporation) in the amounts shown in Table 3 to prepare coating compositions.

[0139] The prepared coating composition was applied to a glass substrate using a coater to a wet film thickness of 152 μm, and the coated substrate was dried at room temperature for one week. In this manner, an algaecide sample consisting of a urethane resin coating and a glass substrate was produced.

[0140] The samples prepared above were subjected to a closed-system algae prevention test based on JIS R1712:2022, and the algae prevention activity values ​​were calculated. The results are shown in Table 2. The algae prevention activity value is a numerical value obtained by quantifying the effect of reducing algae production, with higher values ​​indicating higher algae prevention properties.

[0141] It should be noted that the closed system algae prevention evaluation was performed using the following apparatus and conditions.

[0142] Test subject: Chlorella vulgaris

[0143] Sterilization: Heating in a dry heat sterilizer (80°C, 15 minutes)

[0144] Light source type: White fluorescent lamp (FL20SSW / 18, manufactured by Mitsubishi Electric Lighting Co., Ltd.)

[0145] Illuminance meter: IM-600M (manufactured by TOPCON Co., Ltd.)

[0146] Spectrophotometer: U-5100 (manufactured by Hitachi Hi-Tech Co., Ltd.)

[0147] Sealing film: Polypropylene film (VF-10, KOKUYO), 40mm×40mm

[0148] Moisturizing glass: borosilicate glass

[0149] Inoculation volume of test solution: 0.1 ml

[0150] Concentration of test solution: OD530 = 10.0

[0151] Spectrophotometer setting conditions: Bandpass 5nm

[0152] Irradiation conditions: visible light 500lx, 25±3℃

[0153] Irradiation time: 24 hours

[0154] Chopper filter: Type A (N113, blocks wavelengths below 400 nm)

[0155] The anti-algae activity value was calculated using the following formula.

[0156] W base692 =W 660+(W 750 -W 660 ) / (750-660)×(692-660)

[0157] W peak =W 692 -W base692

[0158] R s1 = (1-W p1 / W n1 ) × 100

[0159] W x : absorbance of the sample at wavelength x [nm]

[0160] W basex : Absorbance of PET substrate at wavelength x [nm]

[0161] R s1 : Anti-algae activity value of the sample

[0162] W p1 : The absorbance of the sample after a given time of light exposure

[0163] W n1 : Absorbance of PET substrate after light irradiation for a given time

[0164] [Table 3]

[0165]

[0166] The metal contents in Table 3 are the metal contents derived from the fatty acid metal salts. For example, in Example 13, the coating composition contained 2.6 parts by mass of lanthanum derived from lanthanum neodecanoate per 100 parts by mass of the resin solid content (urethane resin).

[0167] From the results in Table 3, it can be confirmed that the fatty acid metal salts prepared in Synthesis Example exhibit high anti-algae activity values.

Claims

1. An algaecide for preventing the adhesion of terrestrial algae, comprising a fatty acid metal salt containing a fatty acid having 1 to 22 carbon atoms and a metal. The metal is copper, bismuth, zinc, magnesium, cobalt or a rare earth element.

2. The algaecide according to claim 1, wherein The fatty acid is 2-ethylhexanoic acid, neodecanoic acid, isononanoic acid, cycloalkane acid, lauric acid, stearic acid, isostearic acid or palmitic acid.

3. The algaecide according to claim 1, wherein The metal is bismuth or a rare earth element. An anti-algae coating composition comprising the anti-algae agent according to any one of claims 1 to 3 and a binder resin.

5. The anti-algae coating composition according to claim 4, wherein The binder resin is one or more selected from acrylic resin, vinyl acetate resin, styrene resin, vinyl chloride resin, olefin resin, carbamate resin, urea-formaldehyde resin, carbamate urea-formaldehyde resin, epoxy resin, melamine resin, phenolic resin, polyester resin, alkyd resin, silicone resin, acrylonitrile / styrene copolymer resin and acrylonitrile / butadiene copolymer resin.

6. The anti-algae coating composition according to claim 4, wherein The metal derived from the anti-algae agent is contained in an amount within a range of 0.01 to 30 parts by mass based on 100 parts by mass of the resin solid content. 7 . A laminate comprising a coating layer of the anti-algae coating composition according to claim 4 and a substrate.

8. A building comprising a coating of the anti-algae coating composition according to claim 4 on its outer wall and / or inner wall. 9 . An anti-algae resin composition comprising the anti-algae agent according to claim 1 and a resin. 10 . A molded article obtained by molding the anti-algae resin composition according to claim 9 .

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