Composition for pest control

Abstract

The present invention addresses the problem of providing a silver-containing harmful organism control composition that is insusceptible to coloration.　The harmful organism control composition according to the present invention contains the following components (A), (B), and (C). (A) A nitrogen-containing heterocyclic compound represented by formula (1) and / or a salt thereof (in formula (1), X is a nitrogen atom or a substituted or unsubstituted carbon atom, Y is a nitrogen atom or a substituted or unsubstituted carbon atom, and Z is a substituted or unsubstituted carbon atom; when Y is a carbon atom, Y and Z together may form a substituted or unsubstituted benzene ring or a substituted or unsubstituted 6-membered heterocycle); (B) One or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper; and (C) a silver component.

Description

Technical Field

[0001] The present invention relates to a pest control composition containing silver. This application claims priority to Japanese Patent Application No. 2021-118193 filed on July 16, 2021, the content of which is incorporated herein by reference.

Background Art

[0002] Silver is widely used in bactericides, disinfectants, antibacterial agents, preservatives, antiviral agents, algicides, etc. because of its high safety. However, silver generally easily undergoes chemical changes. For example, it is reduced and deposited by ultraviolet rays, or reacts with chloride ions to precipitate insoluble silver chloride. As a result, problems such as discoloration and coloring occur, and it has been a problem that the commercial value is visually impaired. For example, Patent Document 1 describes that a compound formed by binding a triazole or its derivative and silver ions can suppress the coloring of silver. Patent Document 2 describes an antibacterial and antifungal agent characterized by containing, as an active ingredient, a compound formed by binding a nucleobase and silver ions.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a pest control composition containing silver with reduced coloring and less likely to cause color tone changes.

Means for Solving the Problems

[0005] As a result of repeated studies to achieve the above object, the present inventors have found that by containing a specific nitrogen-containing heterocyclic compound and / or a salt thereof, one or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper, and a silver component, a pest control composition containing silver and being less likely to cause coloring can be provided, and thus the present invention has been completed.

[0006] That is, the present invention includes the following aspects. [1] A pest control composition containing (A) a nitrogen-containing heterocyclic compound represented by formula (1) and / or a salt thereof, [Chemical formula] (In formula (1), X is a nitrogen atom or a substituted or unsubstituted carbon atom, Y is a nitrogen atom or a substituted or unsubstituted carbon atom, and Z is a substituted or unsubstituted carbon atom. When Y is a carbon atom, Y and Z may together form a substituted or unsubstituted benzene ring or a substituted or unsubstituted 6-membered heterocycle.) (B) one or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper, and (C) a silver component. [2] The pest control composition according to [1], wherein the molar ratio of the nitrogen-containing heterocyclic compound represented by formula (1) to one or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper and the silver component is 10:1 to 1:4. [3] The pest control composition according to [1] or [2], wherein the content ratio of the silver component is equimolar or more with respect to one or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper. [4] The pest control composition according to any one of [1] to [3], wherein the nitrogen-containing heterocyclic compound represented by formula (1) is any one of 1,2,4-triazole, methyltetrazole, benzotriazole, xanthine, hypoxanthine, and methylbenzotriazole. [5] The pest control composition according to any one of [1] to [4], wherein at least one metal component selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper is a zinc component. [6] The pest control composition according to any one of [1] to [5], wherein the composition containing a nitrogen-containing heterocyclic compound represented by the formula (1), at least one metal selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper, and silver is a complex. [7] A resin molded article containing the pest control composition according to any one of [1] to [6]. [8] A paint containing the pest control composition according to any one of [1] to [6]. [9] A pest control composition containing at least one of the pest control composition according to any one of [1] to [6] and other industrial biocides.

Advantages of the Invention

[0007] The pest control composition of the present invention reduces the coloring that may be caused by the contained silver, and the color tone change is unlikely to occur. For example, even in the presence of chloride ions, coloring due to silver chloride precipitation is unlikely to occur. Nevertheless, the biological activity is maintained. Compositions containing silver have had the problem that it is difficult to achieve both activity and coloring suppression, but the composition of the present invention can solve this problem. Therefore, the pest control composition of the present invention is particularly useful for applications in fields where silver has been a problem with coloring. In addition, since the amount of silver used can be suppressed, the price may also be suppressed.

Brief Description of the Drawings

[0008]

Figure 1

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BEST MODE FOR CARRYING OUT THE INVENTION

[0009] (Pest control composition) The pest control composition of the present invention comprises (A) A nitrogen-containing heterocyclic compound represented by formula (1) and / or a salt thereof, (B) One or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper, and (C) A silver component.

[0010] The composition of the present invention may be in any form as long as it contains the above components (A), (B), and (C). At least a part of the above components (A), (B), and (C) forms a reaction product, but unreacted raw materials may be present. Preferably, all are reaction products. Although the structure of the reaction product has not been determined, it is considered to form a complex. In the present invention, the "metal component" and the "silver component" include metal atoms and silver atoms present in the reaction product, and metal salts and silver salts derived from raw materials when they are present.

[0011] (Component (A) (Nitrogen-containing heterocyclic compound and / or its salt)) The nitrogen-containing heterocyclic compound is represented by formula (1).

CHEMICAL FORMULA

[0012] Examples of the substituent on the carbon in X include C1-C6 alkyl groups such as methyl group and ethyl group. Examples of the substituent on the carbon atoms of Y and Z include C1-C6 alkyl groups such as methyl group and ethyl group; hydroxyl group; amino group; C1-C6 alkylamino groups such as methylamino group and ethylamino group; carboxamide group, etc. The 6-membered heterocyclic ring is an aromatic heterocyclic ring or an unsaturated heterocyclic ring having a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom. As the 6-membered heterocyclic ring, a nitrogen-containing ring is preferably used, and examples thereof include pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. Examples of the substituent on the 6-membered heterocyclic ring include the substituents exemplified as the substituents on the carbon atoms of X, Y, and Z, and also include an oxo group (=O), etc. As the nitrogen-containing heterocyclic ring compound represented by formula (1) used in the present invention, any one of 1,2,4-triazole (1,2,4-TAZ), methyltetrazole, benzotriazole, xanthine, hypoxanthine, and methylbenzotriazole is particularly preferred. Examples of the salt of the nitrogen-containing heterocyclic ring compound represented by formula (1) include salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid; salts of alkali metals such as lithium, sodium, and potassium; salts of alkaline earth metals such as calcium and magnesium; salts of transition metals such as iron and copper; salts of organic bases such as triethylamine, tributylamine, pyridine, and hydrazine; ammonium salts, etc.

[0013] (Component (B) (metal component)) The pest control composition of the present invention contains one or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper. Among these, it is particularly preferable to contain zinc. These metal components can be used alone or in combination of two or more. The metal component is derived from those added as metal salts as raw materials, and in the case where the above nitrogen-containing heterocyclic compound is an aluminum, calcium, magnesium, zinc, or copper salt, the metal component derived therefrom is also included.

[0014] (Component (C) (silver component)) It is the active body of the pest control composition of the present invention. In order to fully exhibit biological activity, it is preferable that the silver component is contained in an equimolar amount or more compared to the total amount of one or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper.

[0015] (Composition ratio) In the pest control composition of the present invention, the total of the nitrogen-containing heterocyclic compound, one or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper, and the silver component is preferably in a molar ratio of 10:1 to 1:4, more preferably 10:1 to 1:3, and even more preferably 10:1 to 1:2.

[0016] (Preparation of pest control composition) The pest control composition of the present invention is obtained by mixing, in a solvent, a nitrogen-containing heterocyclic compound and / or its salt, a silver salt dissolved in an appropriate solvent, and one or more metal salts selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper (hereinafter also referred to as "other metal salts"). As the silver salt and other metal salts as raw materials, any known ones can be used without limitation according to the type of solvent. For example, inorganic salts such as nitrates, hydrochlorides, phosphates, and sulfates; organic acid salts such as acetates, oxalates, citrates, and benzoates can be mentioned. Among these, nitrates and the like can be preferably used.

[0017] The solvent used may be of any type as long as it can dissolve the nitrogen-containing heterocyclic compound and / or its salt, silver salt, and other metal salts and is difficult to dissolve the product. For example, water; organic acids such as formic acid, acetic acid, lactic acid, oxalic acid, citric acid, benzoic acid; alcohols such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, n-butanol; amines such as ethanolamine, dimethylamine, pyridine; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetylacetone; ethers such as diethyl ether, dimethyl ether, tetrahydrofuran; ether group-containing alcohols such as ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, ethyl lactate, butyl lactate; hydrocarbons such as hexane, benzene, xylene, toluene; halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chloroform, trichloroethylene; acetonitrile; mineral oil, synthetic hydrocarbon oil, synthetic ester oil, natural oil, natural oil derivative, ether oil, silicone oil, fluorine oil, etc. These solvents may be used alone or in combination of two or more. From the perspective of manufacturing cost and subsequent treatment, the solvent is particularly preferably water.

[0018] The conditions during mixing are as follows. The mixing ratio of the nitrogen-containing heterocyclic compound and / or its salt to the silver salt and other metal salts during preparation is preferably in the range of a molar ratio of nitrogen-containing heterocyclic compound and / or its salt: silver salt and other metal salts = 1:20 to 20:1, and more preferably in the range of a molar ratio of 1:15 to 5:1. The mixing ratio of the silver salt to the other metal salts during preparation is preferably in the range of a molar ratio of silver salt: other metal salts = 20:1 to 1:20, and more preferably in the range of 10:1 to 2:1. The reaction can be carried out at any temperature and time.

[0019] When carrying out the reaction in a solvent, the molar concentration of the silver salt and other metal salts in the solvent is preferably 0.005 to 5 mol / L, more preferably 0.01 to 2 mol / L. The molar concentration of the nitrogen-containing heterocyclic compound and / or its salt is preferably 0.001 to 5 mol / L, more preferably 0.005 to 2 mol / L.

[0020] The pest control composition of the present invention may be simply prepared by mixing a nitrogen-containing heterocyclic compound and / or its salt, other metal salts and silver salts, but it may also be placed in a pressure-resistant container such as an autoclave and reacted under high temperature and pressure. The heating temperature of the reaction solution is not particularly limited as long as a composition capable of exerting the effects of the present invention can be obtained, but the range of room temperature to 200 °C is preferred. When heating, it is preferably 100 to 150 °C.

[0021] The reaction time of this production method is not particularly limited as long as a composition capable of exerting the effects of the present invention can be obtained, but in terms of better yield of the composition, 1 hour to 1 week is preferred.

[0022] A basic compound can be used in the preparation of the pest control composition of the present invention. The basic compound has the function of anionizing the nitrogen-containing heterocyclic compound and making it easier to react with the metal salt. The type of the basic compound is not particularly limited, and known basic compounds can be used. Examples of the basic compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, hydroxides of alkaline earth metals such as barium hydroxide and calcium hydroxide, carbonates such as sodium carbonate, potassium carbonate, and sodium hydrogen carbonate, and amine compounds such as triethylamine and diisopropylethylamine. Among them, sodium hydroxide is preferred because of its easy solubility in the solvent. This is not the case when using a salt of a nitrogen-containing heterocyclic compound as a raw material.

[0023] The procedure of this manufacturing method is not particularly limited as long as a composition capable of achieving the effects of the present invention can be obtained. For example, a method of mixing a nitrogen-containing heterocyclic compound and / or its salt, a silver salt, and other metal salts in the presence of a solvent and a basic compound is preferably mentioned. More specifically, a method of adding a silver salt and other metal salts dissolved in an appropriate solvent and, if necessary, a basic compound to a nitrogen-containing heterocyclic compound and / or its salt dissolved in an appropriate solvent and reacting them is mentioned. In this manufacturing method, the method of mixing the reaction substrates is not particularly limited, and known methods can be adopted. Also, the order of adding each component is not particularly limited, and the above components may be added to the reaction vessel simultaneously or in order.

[0024] After the reaction is completed, the product and the solvent in the above reaction system can be easily separated by a separation method such as filtration or centrifugation. In addition, the product prepared in the above process can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these separation means.

[0025] The structure, composition, and performance of the pest control composition of the present invention can be confirmed using general methods. For example, it can be carried out using X-ray diffraction measurement (confirmation of crystal structure), 13C-CPMAS-NMR and 15N-CPMAS-NMR (structural analysis of the product), thermal analysis (measurement of heat resistance), ICP and elemental analysis (confirmation of composition), MIC test (confirmation of performance), etc.

[0026] The pest control composition of the present invention shows different behaviors from Comparative Examples 1 and 2 by X-ray diffraction method (XRD), X-ray photoelectron spectroscopy (XPS), thermal analysis, nuclear magnetic resonance spectrum measurement, etc. It is considered that a complex is formed rather than a physical mixture of Comparative Examples 1 and 2.

[0027] (Optional components that can be used together with the pest control composition of the present invention) The pest control composition of the present invention can be used together with other components by adding other components or adding them to other components according to the application. Examples of other components include resins, solvents, surfactants, coupling agents, fillers, insecticides, fungicides, herbicides, plant growth regulators, industrial biocides, and the like.

[0028] (Resin) The pest control composition of the present invention can be used together with various resins according to the application, required performance, and the like. Examples of resins include thermoplastic resins, thermosetting or photocurable resins, and the like. These may be used alone or in combination of two or more. Examples of the thermoplastic resin include styrene resins, acrylic resins, vinyl acetate resins, acrylonitrile copolymers, polyphenylene oxide resins, polysulfone resins, polyethersulfone, polyarylate, polyetherimide, polyamideimide, polyimide, polymethyl methacrylate, acrylonitrile-styrene copolymer resins, acrylonitrile-styrene-N-substituted maleimide terpolymers, acrylonitrile-butadiene-styrene copolymer resins, styrene-maleic anhydride copolymer resins, styrene-maleic anhydride-N-substituted maleimide copolymer resins, polycarbonate resins, polybutylene terephthalate resins, polyethylene (such as linear low density polyethylene, low density polyethylene, high density polyethylene, etc.), polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polypropylene, styrene-butadiene-styrene block copolymers and their hydrogenated products, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polybutadiene, polyisoprene, styrene-isoprene-styrene block copolymers and their hydrogenated products, polyolefin elastomers, polyester elastomers, polystyrene, acrylic resins, methyl methacrylate-styrene copolymers, acrylonitrile-styrene-methyl methacrylate copolymers, polyacetal resins, modified polyphenylene ether resins, ethylene-vinyl acetate copolymers, polyphenylene sulfide resins, polyphenyl sulfone, polyether ketone, polyether ether ketone, polyethers, cycloolefin polymers, liquid crystal polyester resins, liquid crystal polymers, polyamides, fluorine resins, polyvinyl pyrrolidone, natural rubber, butyl rubber, polyisobutylene, polysulfide, etc.

[0029] The thermosetting resin is one that cures by the progress of a polymerization reaction or a crosslinking reaction upon heating. Examples of the thermosetting resin include phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethanes, thermosetting polyimides, diallyl phthalate resins, etc. It may also be a composition obtained by blending a vulcanizing agent, a curing agent or a crosslinking agent with the thermoplastic resin.

[0030] A photocurable resin is one that cures by the progress of a polymerization reaction or a crosslinking reaction upon irradiation with light such as ultraviolet light. For example, it is obtained by blending a photoinitiator such as a photo radical generator, a photo cation generator, a photo acid generator, or a photo base generator into a desired monomer or oligomer. The monomer or oligomer that can be used in the photocurable resin is not particularly limited, and examples include (meth)acrylate monomers, (meth)acrylate oligomers, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, cyclohexanedimethanol diglycidyl ether 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol; oxetane compounds such as xylylene bisoxetane and 3-ethyl-3-hydroxymethyloxetane; vinyl ether monomers such as cyclohexanedimethanol divinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, and 4-hydroxybutyl vinyl ether.

[0031] Examples of other resins include silicone, acrylic silicone, modified silicone, lacquer, glue, petroleum resin, hydrogenated petroleum resin; starch such as rice, wheat, corn, potato, sweet potato, tapioca, and other natural products, or biodegradable plastics made from these as raw materials.

[0032] When the pest control agent composition of the present invention is used as a resin composition, the amount of the resin contained in the resin composition can be appropriately set according to the use. For example, the amount of the resin in 100 parts by mass of the resin composition can be used in the range of 5 to 99 parts by mass, 30 to 95 parts by mass, or 50 to 90 parts by mass.

[0033] (Solvent) The pest control composition of the present invention can also be used as a composition together with a solvent. The solvent capable of dispersing or dissolving the pest control composition of the present invention may be selected according to the use and is not particularly limited. For example, the same solvents as those exemplified as the solvents in the production examples can be mentioned.

[0034] (Surfactant) The pest control composition of the present invention can also be used as a composition together with a surfactant. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Examples of nonionic surfactants include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene aryl phenyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene vegetable oil, and the like. Examples of anionic surfactants include, for example, alkylbenzene sulfonates, lignin sulfonic acid or its salts, naphthalene sulfonate formaldehyde condensates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, dialkyl sulfosuccinates, and the like. Examples of cationic surfactants include, for example, aliphatic amine salts and quaternary ammonium salts. Examples of amphoteric surfactants include, for example, alkyl betaine type surfactants, amidopropyl betaine type surfactants, imidazolinium betaine type surfactants, sulfobetaine type surfactants, phosphobetaine type surfactants, and the like. The total amount of the surfactant that can be included in the composition of the present invention is not particularly limited. For example, it can be used in the range of 2 to 100 parts by mass and 15 to 30 parts by mass with respect to 100 parts by mass of the nitrogen-containing heterocyclic compound and / or its salt.

[0035] (Coupling agent) Examples of coupling agents include silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, etc. Examples of silane coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.

[0036] Examples of titanate coupling agents include titanium alkoxides such as tetraisopropyl titanate, tetra-n-butyl titanate, tetrakis(2-ethylhexyloxy)titanium, titanium-i-propoxy octylene glycolate; titanium complexes such as titanium acetylacetonate, titanium tetraacetylacetonate, di-i-propoxy·bis(acetylacetonato)titanium, di-n-propoxy·bis(acetylacetonato)titanium, di-n-butoxy·bis(acetylacetonato)titanium, diethoxy·bis(acetylacetonato)titanium, propanedioxytitanium bis(ethylacetoacetate), etc.

[0037] Examples of aluminate coupling agents include aluminum alcoholates such as aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, and aluminum ethylate; aluminum complexes such as diisopropyl aluminum ethylacetoacetate, aluminum bis(ethylacetoacetate)·monoacetylacetonate, aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), diethoxymono(acetylacetonate) aluminum, di-i-propoxymono(acetylacetonate) aluminum, di-n-propoxymono(acetylacetonate) aluminum, di-n-butoxymono(acetylacetonate) aluminum, ethoxybis(acetylacetonate) aluminum, i-propoxybis(acetylacetonate) aluminum, n-propoxybis(acetylacetonate) aluminum, and n-butoxybis(acetylacetonate) aluminum; and cyclic aluminum oligomers.

[0038] Examples of zirconate coupling agents include zirconium tetrakis(acetylacetonate), di-n-butoxybis(acetylacetonate) zirconium, zirconium tetrakis(ethylacetoacetate), diethoxybisacetylacetonate zirconium, di-i-propoxybis(acetylacetonate) zirconium, di-n-propoxybis(acetylacetonate) zirconium, tri-n-butoxymonoethylacetoacetate zirconium, and tri-n-butoxymonoacetylacetonate zirconium.

[0039] (Filler) Examples of fillers include carbon black, graphene, carbon nanotubes, glass fibers, iron oxide, barite, talc, calcium carbonate, kaolin, clay, silica, titanium dioxide, alumina, zirconia, silicone resin fine particles, fluororesin fine particles, acrylic resin fine particles, urethane resin fine particles, silicone-modified urethane resin fine particles, polyethylene fine particles, and polycarbonate resin fine particles.

[0040] (Insecticides, fungicides, herbicides, plant growth regulators, industrial biocides, etc.) The pest control composition of the present invention can also be used as a composition together with fungicides, insecticides, herbicides, plant growth regulators, industrial biocides, etc. These components can be used without particular limitation. The active ingredient to be used may be liquid or solid, may be an organic compound or an inorganic compound, and may be a single compound or a mixture. Specific examples are shown below. Insecticides include pyrethroid compounds such as cyfluthrin, cypermethrin, deltamethrin, fenpropathrin, fenvalerate, esfenvalerate, tralomethrin, acrinathrin, bifenthrin, resmethrin, tetramethrin, tefluthrin, etofenprox, silafluofen, phenothrin, permethrin, prallethrin, pyrethrin; carbamate compounds such as propoxur, isoprocarb, xylylcarb, methiocarb, XMC, carbaryl, pyrimicarb, carbofuran, mesomil, phenoxycarb, alanicarb, methoxadiazone; organophosphorus compounds such as acephate, fenthoate, bamidothion, trichlorfon, monocrotophos, tetrachlorvinphos, dimethylvinphos, hosalone, chlorpyrifos, chlorpyrifos-methyl, pyridaphenthion, quinalphos, methidathion, methamidophos, dimethoate, fenthion, azinphos-ethyl, azinphos-methyl, salithion, fenitrothion; urea compounds such as diflubenzuron, chlorfluazuron, lufenuron, hexaflumuron, flufenoxuron, flucycloxuron, cyromazine, diafenthiuron, hexythiazox, novaluron, teflubenzuron, triflumuron, 4-chloro-2-(2-chloro-2-methylpropyl)-5-(6-iodo-3-pyridylmethoxy)pyridazin-3(2H)-one, 1-(2,6-difluorobenzoyl)-3-[2-fluoro-4-(trifluoromethyl)phenyl]urea, 1-(2,6-difluorobenzoyl)-3-[2-fluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]urea, 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazin-4-one, 1-(2,6-difluorobenzoyl)-3-[2-fluoro-4-(1,1,2,2-tetrafluoroethoxy)phenyl]urea; neonicotinoid compounds such as imidacloprid, acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, thiacloprid, dinotefuran;Examples include fipronil, cartap, buprofezin, thicyclam, bensultap, phenoxycarb, phenothrin, fenpyroximate, pyridaben, pyriproxyfen, hydramethylnon, thiodicarb, phenobucarb, chlorfenapyr, fenproximate, pymetrozine, pyrimidifen, tebufenozide, tebufenpyrad, methoxyfenozide, triazamate, indoxacarb, sulfluramid, milbemectin, abamectin, chlorantraniliprole, pyriprole, broflanilide, flupyradifurone, dichloromethothiaz, boric acid, disodium octaborate tetrahydrate, borax, borax pentahydrate, paradichlorobenzene, capric acid, and the like.;

[0041] Examples of fungicides include benzimidazole compounds such as benomyl, carbendazim, thiabendazole, and thiophanate-methyl; phenylcarbamate compounds such as diethofencarb; dicarboximide compounds such as procymidone, iprodione, and vinclozolin; azole compounds such as triflumizole, hexaconazole, diniconazole, epoxiconazole, tebuconazole, difenoconazole, cyproconazole, propiconazole, flusilazole, triadimefon, metconazole, myclobutanil, imazalil, and triforine; acylalanine compounds such as metalaxyl; carboxamide compounds such as flutolanil, mepronil, flutolanil, and triflumizole; organophosphorus compounds such as tolclofos-methyl, fosetyl-aluminum, and pyrazophos; anilinopyrimidine compounds such as pyrimethanil, mepanipyrim, and cyprodinil; cyanopyrrole compounds such as fluazinam and fenpiclonil; antibiotics such as blasticidin S, kasugamycin, polyoxin, and validamycin; methoxyacrylate compounds such as azoxystrobin, pyraclostrobin, trifloxystrobin, kresoxim-methyl, and SSF-126; iminoctadine acetate, iminoctadine albesilate, penflufen, chlorothalonil, mancozeb, captan, folpet, copper oxinate, basic copper chloride, tricyclazole, pyroquilon, probenazole, fusaride, simoxanil, dimethomorph, CGA245704, famoxadone, oxolinic acid, fluazinam, ferimzone, clobenpropit, isovaledione, thophthalimide oxybisphenoxarsine, 3-iodo-2-propyl butylcarbamate, and the like.

[0042] Examples of herbicides include triazine compounds such as atrazine and metribuzin; urea compounds such as fluometuron and isoproturon; hydroxybenzonitrile compounds such as bromoxynil and ioxynil; 2,6-dinitroaniline compounds such as pendimethalin and trifluralin; aryloxyalkanoic acid compounds such as 2,4-D, dicamba, fluroxypyr, and mecoprop; sulfonylurea compounds such as bensulfuron-methyl, metsulfuron-methyl, nicosulfuron, primisulfuron-methyl, and cyclosulfamuron; imidazolinone compounds such as imazapyr, imazakine, and imazethapyr; bispyribac Na salt, bisthiobac Na salt, asiflurofen Na salt, sulfentrazone, paraquat, flumeturon, triflusulfuron-methyl, fenoxaprop-p-ethyl, cyhalofop-butyl, difufenican, norflurazon, isoxaflutole, glufosinate ammonium salt, glyphosate, bentazone, benthiocarb, mefenacet, propanil, fluthiamide, and the like.

[0043] Examples of plant growth regulators include maleic hydrazide, chloromequat, ethephon, gibberellin, mepiquat chloride, thidiazuron, inabenfide, paclobutrazol, uniconazole, and the like. Examples of insect repellents include 1S,3R,4R,6R-carane-3,4-diol, dipropyl 2,5-pyridinedicarboxylate, and the like.

[0044] Examples of industrial biocides include the aforementioned agricultural and horticultural chemicals, fungicides, preservatives, algaecides, or wood preservatives, etc. Quaternary ammonium salt compounds such as didecyldimethylammonium chloride (DDAC), didecyldimethylammonium adipate (DDAA), benzalkonium chloride, N,N-didecyl-N-methyl-polyoxyethyl-ammonium propionate (DMPAP), N,N-didecyl-N,N-dimethylammonium bicarbonate, N,N-didecyl-N,N-dimethylammonium carbonate; biguanide compounds such as polyhexamethylene biguanide (PHMB), polyhexamethylene guanidine (PHMG), chlorhexidine gluconate; pyridinium compounds such as cetylpyridinium chloride, dodecylpyridinium chloride; organic iodine compounds such as 3-iodo-2-propynyl-butylcarbamate (IPBC); pyridine compounds such as 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine (TCMSP); pyrithione compounds such as zinc pyrithione, sodium pyrithione; benzothiazole compounds such as 2-(4-thiocyanomethylthio)benzothiazole; imidazole compounds such as methyl-2-benzimidazole carbamate, 2-(4-thiazolyl)-benzimidazole; thiocarbamate compounds such as tetramethylthiuram disulfide; nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile; haloalkylthio compounds such as N-(fluorodichloromethylthio)-phthalimide, N-(fluorodichloromethylthio)-N,N’-dimethyl-N-phenyl-sulfamide; triazole compounds such as α-t-butyl-α(p-chlorophenylethyl)-1H-1,2,4-triazole-1-ethanol (common name tebuconazole); isothiazolone compounds such as 1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazol-3(2H)-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 4,Isothiazoline compounds such as 5-dichloro-2-cyclohexyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-t-octyl-4-isothiazolin-3-one, 2-n-butyl-1,2-benzisothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, bromine compounds such as 2-bromo-2-nitro-1,3-propanediol, 2,2-dibromo-2-nitroethanol, 2,2-dibromo-3-nitrilopropionamide, parachlorometacresol, 4-chloro-3,5-xylenol, triazine-1,3,5(2H,4H,6H)-triethanol, streptomycin, diuron (DCMU), dimefuron, metobenzuron, cumyluron, nicosulfuron, linuron, cyprazine, terbutryne, simazine, atrazine, propazine, cyanazine, dimethamethrin, promethrin, butralin, benfluralin, prodiamine, benzofenap, pyraflufen-ethyl, biphenox, bromobutide, bromoxynil, propanil, diflufenican, mefenacet, chlormeprop, diclomezine, dithiopyr, isoxaben, lenacil, pyributicarb, pyriminobac-methyl, oxadiazon, oryzalin, oxadiargyl, fluthiacet-methyl, pyribenzoxim, pentoxazone, silver zeolite, silver silica gel, silver salt of zirconium phosphate, silver complex of histidine, para-hydroxybenzoic acid ester, sodium benzoate, sodium dehydroacetate, potassium sorbate, methylparaben, methylene bisthiocyanate, cupric oxide, cupric hydroxide, creosote oil, lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, etc. can be mentioned.,

[0045] (Others) The pest control composition of the present invention can be used as a composition by adding various components as needed or adding to various components, as long as the effects of the present invention are not impaired. Such components include flame retardants, heat stabilizers, antioxidants, lubricants, antistatic agents, ultraviolet light absorbers, colorants, mold release agents, heat insulating agents, dispersants, pH adjusters, defoamers, rust preventives, viscosity adjusters, sequestering agents, friction adjusters, and the like. Two or more of these can also be used in combination.

[0046] (Use) The pest control composition of the present invention exhibits antimicrobial activities such as antiseptic activity, antibacterial activity, antifungal activity, antiviral activity, and anti-algal activity. Therefore, it can be suitably used for various materials that require antimicrobial properties, whether in solid products or liquid products. For example, it can also be preferably used to impart pest control activity to paints, resin emulsions, aqueous waxes, joint materials, sealing materials, cement admixtures, adhesives, glues, varnishes, pigments, inks, fibers, pulp, rubbers, latexes, adhesives, films, formulations, ceramic materials, metalworking fluids, dyes, wetting water for printing, surface sizing agents, coating liquids for paper, papermaking chemicals, heat-sensitive and pressure-sensitive paints, fiber processing chemicals, detergents, coating agents, various industrial waters, freshness-retaining liquids for cut flowers, and bath water.

[0047] (Use as resin molded articles, paints, glues, varnishes, etc.) The pest control composition of the present invention can be used as it is, but if necessary, it can be mixed with resins, solvents, water, etc. to prepare various compositions, thereby obtaining resin molded articles, paints, glues, varnishes, resin emulsions, aqueous waxes, rubber latexes, joint materials, sealing materials, cement admixtures, adhesives, adhesives, pigment dispersions, dye solutions, wetting water for printing, surface sizing agents, coating liquids for paper, papermaking chemicals, heat-sensitive and pressure-sensitive dyes, fiber processing chemicals, detergents, coating agents, metalworking fluids, various industrial waters, freshness-retaining liquids for cut flowers, and bath water bactericidal liquids. In the case of resin molded articles, paints, etc., they may contain additives which are conventionally known constituent components. For example, they may contain fillers, pigments, dyes, curing agents, polymerization inhibitors, mold release agents, thickeners, viscosity reducers, defoaming agents, foaming agents, anti-separation agents, leveling agents, plasticizers, emulsifiers, desiccants, solvents, glass fibers, carbon fibers, surfactants. The mixing method can be a conventionally known method. For example, in the case of using a resin, it can be produced by melt-kneading. Specifically, a predetermined amount of a thermoplastic resin, a nitrogen-containing heterocyclic compound and / or its salt, a silver component and other metal components, and other additive components optionally blended are weighed, mixed using various mixers such as a tumbler or a Henschel mixer, and then melt-kneaded using a Banbury mixer, rolls, a plapender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, etc.

[0048] As a method for molding a resin molded article, conventionally known methods for molding a molded article from a thermoplastic resin material can be applied without limitation. Specifically, general injection molding methods, ultra-high-speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using a heat-insulating mold, molding methods using a rapidly heated mold, foam molding (including supercritical fluids), insert molding, in-mold coating (IMC) molding methods, extrusion molding methods, sheet molding methods, thermoforming methods, rotational molding methods, lamination molding methods, press molding methods, etc. can be mentioned.

[0049] When the pest control composition of the present invention is used in a paint, it may be a resin composition obtained by blending the pest control composition with a resin, and the resin composition may contain the above additives. Further, it may contain a solvent or water for imparting fluidity. Also, it may be a commercially available paint added with the pest control composition of the present invention. The articles to be painted with the paint are not particularly limited. For example, articles used for around water in housing equipment such as outer wall surfaces, inner wall surfaces, painted parts, kitchen utensils, articles around bathrooms, etc. can be mentioned. The painting method is not particularly limited. For example, application by dipping, brushing, roller, spraying, coater, etc. can be mentioned.

[0050] When the pest control composition of the present invention is used as a resin emulsion, an aqueous wax, a rubber latex, a joint material, a sealing material, a cement admixture, an adhesive, a pressure-sensitive adhesive, a pigment dispersion, a dye solution, a dampening water for printing, a surface sizing agent, a paper coating liquid, a papermaking chemical, a thermosensitive and pressure-sensitive dye, a fiber processing chemical, a detergent, a coating agent, a metalworking oil, various industrial water, a freshness-retaining liquid for cut flowers, or a hot water sterilizing liquid for a bathtub, it may be a composition obtained by blending the pest control composition with water or a solvent, and the composition may further contain the above other components.

[0051] When the pest control composition of the present invention is used as a resin composition, the resin composition and its molded products exhibit antimicrobial activities such as antiseptic activity, antibacterial activity, antifungal activity, and antiviral activity. Therefore, for applications requiring antimicrobial properties, for example, spray containers, kitchen utensils and other water-related products, food packaging materials, household products such as cover cloths and garbage covers; sanitary products such as rubber footwear; building materials such as bathroom interiors, floor mats, wall sheets, wallpapers, shoji papers, floor materials, sealing agents, adhesives, and paints; exterior building materials such as resin siding, ceramic siding, and tiles; absorbent fiber products such as diapers, napkins, and incontinence pads, and medical and hygienic products such as gowns and surgical gowns; toilet products such as disposable toilets and toilet covers; pet products such as pet sheets, pet diapers, and pet towels; materials for household electrical appliances such as air purifier filters, air conditioners, humidifiers, and dehumidifiers; packaging containers and food and beverage packages; pharmaceutical packaging materials, ophthalmic drug containers, contact lenses, spectacle lenses, intraocular lenses, and dental and medical materials such as oral treatment tools, bedding, socks, and underwear; housing members such as the exterior materials of personal computers and tablet terminals; cosmetic materials such as foundation containers; toys for infants; stationery; toys; surface film materials for mobile phones and smartphones; water filtration materials; materials that people touch such as keyboards, mice, handrails, and push buttons, etc., can be suitably used.

[0052] Examples are shown below, but the technical scope of the present invention is not limited thereto.

Examples

[0053] Example 1: AgZn-TAZ 7.5 mmol of 1,2,4-triazole (hereinafter referred to as TAZ) dissolved in distilled water, an aqueous silver nitrate solution, and an aqueous zinc nitrate solution were added to a 50 ml vial in a total amount of 7.5 mmol (silver:zinc = 9:1 (molar ratio)), and the mixture was stirred at room temperature for 1 hour. Then, 1 M sodium hydroxide was added, and the mixture was further stirred at room temperature for 1 hour. Thereafter, centrifugation was performed, and the precipitate was washed several times with water and acetone, and dried in vacuo to obtain a white powder.

[0054] Example 2: AgZn-TAZ When the ratio of silver to zinc was 8:2 (molar ratio) and the synthesis was carried out in the same manner as in Example 1, a white powder was obtained.

[0055] Example 3: AgZn-TAZ When the ratio of silver to zinc was 7:3 (molar ratio) and the synthesis was carried out in the same manner as in Example 1, a white powder was obtained.

[0056] Example 4: AgZn-TAZ When the ratio of silver to zinc was 6:4 (molar ratio) and the synthesis was carried out in the same manner as in Example 1, a white powder was obtained.

[0057] Example 5: AgZn-TAZ When the ratio of silver to zinc was 5:5 (molar ratio) and the synthesis was carried out in the same manner as in Example 1, a white powder was obtained.

[0058] Example 6: AgZn-TAZ When the ratio of silver to zinc was 1:9 (molar ratio) and the synthesis was carried out in the same manner as in Example 1, a white powder was obtained.

[0059] Example 7: AgZn-TAZ When the ratio of silver to zinc was 97.5:2.5 (molar ratio) and the synthesis was carried out in the same manner as in Example 1, a white powder was obtained.

[0060] Example 8: AgZn-methyltetrazole 1,2,4-triazole was changed to methyltetrazole and synthesized in the same manner as in Example 3, and a white powder was obtained.

[0061] Example 9: AgZn - benzotriazole 1,2,4-triazole was changed to benzotriazole and synthesized in the same manner as in Example 3, and a white powder was obtained.

[0062] Example 10: AgZn - xanthine To a 50 ml vial, 1M sodium hydroxide was added to 7.5 mmol of xanthine dissolved in distilled water, and a total of 7.5 mmol of silver nitrate aqueous solution and zinc nitrate aqueous solution (silver:zinc = 7:3 (molar ratio)) were added, and the mixture was stirred at room temperature for 1 hour. Then, centrifugation was performed, and it was washed several times with water and acetone respectively, and dried in vacuo to obtain a yellow powder.

[0063] Example 11: AgZn - hypoxanthine Xanthine was changed to hypoxanthine and synthesized in the same manner as in Example 10, and a white powder was obtained.

[0064] Example 12: AgZn - methylbenzotriazole 1,2,4-triazole was changed to methylbenzotriazole and synthesized in the same manner as in Example 3, and a white powder was obtained.

[0065] Example 13: AgCa - TAZ An aqueous calcium nitrate solution was used instead of the aqueous zinc nitrate solution, The ratio of silver:calcium was 7:3 (molar ratio), and when synthesized in the same manner as in Example 3, a white powder was obtained.

[0066] Example 14: AgMg - TAZ An aqueous magnesium nitrate solution was used instead of the aqueous zinc nitrate solution, The ratio of silver:magnesium was 7:3 (molar ratio), and when synthesized in the same manner as in Example 3, a white powder was obtained.

[0067] Example 15: AgAl - TAZ An aluminum nitrate aqueous solution was used instead of the zinc nitrate aqueous solution, and when synthesized in the same manner as in Example 3 with the ratio of silver:aluminum being 7:3 (molar ratio), a white powder was obtained.

[0068] Example 16: AgCu-TAZ A copper nitrate aqueous solution was used instead of the zinc nitrate aqueous solution, and when synthesized in the same manner as in Example 1 with the ratio of silver:copper being 9:1 (molar ratio), a light blue powder was obtained.

[0069] Comparative Example 1: Ag-TAZ When synthesized in the same manner as in Example 1 with the ratio of silver:zinc being 10:0 (molar ratio), a white powder was obtained.

[0070] Comparative Example 2: Zn-TAZ When synthesized in the same manner as in Example 1 with the ratio of silver:zinc being 0:10 (molar ratio), a white powder was obtained.

[0071] Comparative Example 3: AgZn-uracil When 1,2,4-triazole was changed to uracil and synthesized in the same manner as in Example 3, a gray powder was obtained.

[0072] Comparative Example 4: AgZn-cytosine When xanthine was changed to cytosine and synthesized in the same manner as in Example 10, a white powder was obtained.

[0073] Comparative Example 5: AgZn-uric acid When xanthine was changed to uric acid and synthesized in the same manner as in Example 10, a black powder was obtained.

[0074] Comparative Example 6: AgZn-hexamethylenetetramine When 1,2,4-triazole was changed to hexamethylenetetramine and synthesized in the same manner as in Example 3, a black powder was obtained.

[0075] Comparative Example 7: AgZn-melamine 1,2,4-triazole was changed to melamine, and the solvent was changed from water to DMSO. When synthesized in the same manner as in Example 3, a brown powder was obtained.

[0076] Comparative Example 8: Cu-TAZ An aqueous copper nitrate solution was used instead of the aqueous zinc nitrate solution. The ratio of silver to copper was 0:10 (molar ratio). When synthesized in the same manner as in Example 1, a blue powder was obtained.

[0077] (Test) <XRD Analysis> XRD measurements were carried out using a Bruker D2 phaser (CuK radiation) with a solar slit of 4 mm, a divergence slit of 0.4 mm, an air scatter screen of 1 mm, and a step of 0.02°.

[0078] The powder X-ray diffraction data of the compositions obtained in Examples 1, 3, 4, 5, 6, 7 and Comparative Examples 1 and 2 are shown in FIGS. 1 and 2. In each example of the composition of the present invention, a peak (●) specific to AgZn-TAZ is observed. The composition of the present invention is different from Ag-TAZ (Comparative Example 1) or Zn-TAZ (Comparative Example 2).

[0079] When the molar ratio of silver to zinc as raw materials was 1:9 to 97.5:2.5 (Examples 1, 3, 4, 5, 6, 7), the diffraction patterns of Ag-TAZ (Comparative Example 1) or Zn-TAZ (Comparative Example 2) were not confirmed. As the charged amount of silver as the raw material increased, a slight shift of the X-ray diffraction pattern of the product to the low angle side was observed, suggesting an expansion of the lattice due to an increase in the content of silver with a large ionic radius. From the above, it is considered possible that the composition of the present invention is a complex.

[0080] <Elemental Analysis> Elemental analysis of metal components (Ag, Zn) was performed using an ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer). Using a Thermo Fisher Scientific iCAP 7600 Duo system, 0.2 ml of 60% nitric acid was added to 20 mg of the sample, and after preparation to 10 g with pure water, it was appropriately diluted and measurement was carried out. For elemental analysis of non-metal components, a Microcorder JM10 type manufactured by Di·Science·Lab was used. For the measured elements (C, H, N), it was carried out at a sample furnace temperature of 950 °C. Table 1 shows the results of elemental analysis of the powders obtained in each of the examples and comparative examples and the predicted composition of the pest control composition of the present invention.

[0081]

Table 1

[0082] <XPS Analysis> XPS analysis was performed using ULVAC-PHI QuantreraII (Al-Kα). After calibration at Au 4f7 / 2 = 84.00 eV, measurement was carried out. Table 2 and Table 3 (Reference Example) show the results of XPS analysis for the powders obtained in each of the examples and comparative examples and the powder obtained by physically mixing Comparative Example 1 and Comparative Example 2. Incidentally, the physical mixture of Comparative Example 1 and Comparative Example 2 was prepared by collecting each powder at an arbitrary ratio and mixing them in a mortar for 15 minutes. The pest control composition of the present invention has a different value from the comparative example and is different as a substance (Table 2). Also, when Comparative Example 1 and Comparative Example 2 were physically mixed, it was confirmed that there was no difference in value from the original Comparative Example 1 (Table 3). The pest control composition of the present invention is different from the physical mixture of Comparative Example 1 and Comparative Example 2. The pest control composition of the present invention is predicted to be in the form of a complex.

[0083]

Table 2

[0084]

Table 3

[0085] <Solid NMR Analysis> Solid NMR measurements were carried out using a JEOL JNM-ECZ500R NMR / at a sample rotation speed of 12 kHz (15N-NMR) and 20 kHz (13C-NMR). Solid NMR (13C-NMR) data of Examples 3 and 5 and Comparative Examples 1 and 2 and the physical mixture of Comparative Example 1 and Comparative Example 2 are shown in Figure 3. Solid NMR (15N-NMR) data of Example 3, Comparative Examples 1 and 2, and 1,2,4-triazole are shown in Figure 4. Example 5 had different analysis results from the physical mixture of Comparative Example 1 and Comparative Example 2. The pest control composition of the present invention is predicted to be in a complex form. Also, Examples 3 and 5 are different from Comparative Examples 1 and 2.

[0086] <Abuse Test> The powder obtained in Example 4 and the powder obtained in Comparative Example 1 were diffused at 1 mg / ml in 1000 ppm saline, and irradiated with ultraviolet light (0.7 mW / cm 2 ) using a BLB lamp. Photographs after 7 days are shown in Figure 5. The individuals obtained in Example 4 remained white, while the powder obtained in Comparative Example 1 changed to black. It is considered that silver was deposited.

[0087] Similar experiments were also conducted for other examples and comparative examples. The changes in color tone during synthesis and after the abuse test are described in Table 4. It was confirmed that there was no or only minor change in color tone in the examples.

[0088]

Table 4

[0089] <Antibacterial test and antifungal test (MIC test)> Various chemical solutions added with nonionic surfactant Tween 20 or Penetrol N-100 were diluted to a predetermined concentration, and this diluted chemical solution was dispensed into 96-well plate wells, and antibacterial MIC test and antifungal MIC test were conducted under the following conditions. Antibacterial (bacterial MIC) test: An inoculum of cultured bacteria (Staphylococcus aureus subsp. aureus: Staphylococcus aureus) was dropped into the 96-well plate wells dispensed with the chemical solution. It was statically cultured at 31°C in the dark for 7 days, and the MIC (minimum inhibitory concentration) (mg / L), which is the lowest concentration at which no bacterial growth was observed, was determined. The results are shown in Tables 5 to 7. Antifungal (fungal MIC) test: An inoculum in which spores and hyphae obtained by culturing (Aspergillus niger: Aspergillus niger) were dispersed was dropped into the 96-well plate wells dispensed with the chemical solution. It was statically cultured at 26°C in the dark for 7 days, and the MIC (minimum inhibitory concentration), which is the lowest concentration at which no fungal growth was observed, was determined. The results are shown in Tables 5 and 7. Each MIC represents the concentration (mg / L) of the powder in its original form.

[0090]

Table 5

[0091] In the MIC test, the samples obtained in Examples 1, 3, 5, 6, 7 (AgZn-TAZ) and Example 16 (AgCu-TAZ) showed good antibacterial activity and antifungal activity, similar to Ag-TAZ (Comparative Example 1). Among them, Examples 1, 3, 5, 7, and 16 synthesized by charging 50% or more of silver as a metal showed higher activity. The samples obtained in Comparative Example 2 (Zn-TAZ) and Comparative Example 8 (Cu-TAZ) had low antibacterial activity and antifungal activity.

[0092]

Table 6

[0093] In the MIC test, the samples obtained in Example 8 (AgZn - methyltetrazole), Example 9 (AgZn - benzotriazole), Example 10 (AgZn - xanthine), Example 11 (AgZn - hypoxanthine), and Example 12 (AgZn - methylbenzotriazole) also showed good antibacterial activity. These also had suppressed coloring.

[0094]

Table 7

[0095] In the MIC test, the samples obtained in Example 13 (AgCa - TAZ) and Example 14 (AgMg - TAZ) also showed good antibacterial and antifungal activities. These also had suppressed coloring. None of the samples of the examples used in the MIC test showed any color change or only minor color changes even in the abuse test, but it is suggested that by appropriately releasing an appropriate amount of the silver component, each component exerts a good effect against the pests targeted.

[0096] <Antiviral test> A coating film was prepared using the composition obtained in Example 3, and the efficacy against bacteriophage Qβ, influenza virus, and feline calicivirus was confirmed.

[0097] Preparation of Coating Film 1 Using an automatic coating device (PI-1210 manufactured by Tester Sangyo Co., Ltd.), a coating material solution (ethanol: 85.944 Wt%, KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.): 8.74 Wt%, organosilica sol IPA-ST (manufactured by Nissan Chemical Industries, Ltd.): 3.5 Wt%, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone: 0.2 Wt%, Aluminum acetylacetonate: 1.5 Wt%, the composition obtained in Example 3: 0.116 Wt%) was applied to a biaxially stretched polyester (PET) film (Lumirror (R) film, T60 transparent, 250 μm, 148×210 mm) manufactured by Toray Industries, Inc. Then, it was dried in a constant temperature bath at 100°C for 1 minute and cured using an ultraviolet curing light source device (manufactured by Eye Graphics Co., Ltd.).

[0098] Antiviral test (Bacteriophage Qβ) In accordance with JIS R 1756:2020 "Fine Ceramics - Test Method for Antiviral Property of Visible Light Responsive Photocatalyst Materials - Method Using Bacteriophage Qβ", the antiviral test of Coating Film 1 was conducted. However, the test pieces (glass and Coating Film 1) inoculated with the test solution were only left standing in the dark without light irradiation. After inoculating bacteriophage on 5 cm×5 cm glass and Coating Film 1 and leaving it standing for 4 hours, the bacteriophage infectious titer was measured using Escherichia coli. The results are shown in Table 8.

[0099]

Table 8

[0100] In the antiviral test (Bacteriophage Qβ), Coating Film 1 using the composition (AgZn-TAZ) obtained in Example 3 showed good antiviral activity.

[0101] Preparation of Coating Film 2 Using an automatic coating device (PI-1210 manufactured by Tester Sangyo Co., Ltd.), a coating material solution (ethylene glycol monobutyl ether: 85.827 Wt%, KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.): 8.74 Wt%, organosilica sol NMP-ST (manufactured by Nissan Chemical Industries, Ltd.): 3.5 Wt%, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone: 0.2 Wt%, Aluminum acetylacetonate: 1.5 Wt%, the composition obtained in Example 3: 0.233 Wt%) was applied to a biaxially stretched polyester (PET) film (Lumirror (R) film, T60 transparent, 250 μm, 148×210 mm) manufactured by Toray Industries, Inc. Then, it was dried in a constant temperature bath at 100°C for 20 minutes and solidified using an ultraviolet curing light source device (manufactured by Eye Graphics Co., Ltd.).

[0102] Preparation of Coating Film 3 (Blank) Using an automatic coating device (PI-1210 manufactured by Tester Sangyo Co., Ltd.), a coating material solution (ethylene glycol monobutyl ether: 86.06 Wt%, KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.): 8.74 Wt%, organosilica sol NMP-ST (manufactured by Nissan Chemical Industries, Ltd.): 3.5 Wt%, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone: 0.2 Wt%, Aluminum acetylacetonate: 1.5 Wt%) was applied to a biaxially stretched polyester (PET) film (Lumirror (R) film, T60 transparent, 250 μm, 148×210 mm) manufactured by Toray Industries, Inc. Then, it was dried in a constant temperature bath at 100°C for 20 minutes and solidified using an ultraviolet curing light source device (manufactured by Eye Graphics Co., Ltd.).

[0103] Anti-influenza virus test Under the following conditions, an anti-influenza virus test was conducted using Coating Film 2 and Coating Film 3 in accordance with ISO 21702. Virus: Influenza A virus (H3N2) A / Hong Kong / 8 / 68 strain (Influenza A virus, ATCC VR-1679) Host: MDCK cells (ATCC CCL-34) Inoculation: Test virus solution concentration 1.6×10 7 pfu / ml, inoculation volume 0.4 ml Action conditions: Dark place, 25 °C, 0 hours and 24 hours Virus infectivity measurement method: Plaque method

[0104] The results of the anti-influenza virus test are shown in Table 9.

[0105]

Table 9

[0106] In the anti-influenza virus test, Coating film 2 using the composition (AgZn-TAZ) obtained in Example 3 showed good antiviral activity.

[0107] Anti-influenza virus test (with water resistance operation) Coating film 2 and Coating film 3 were each immersed in 50 mL of sterilized distilled water for 18 hours (hereinafter, water resistance operation), and then the test was conducted in the same manner as the anti-influenza virus test. The results of the anti-influenza virus test (with water resistance operation) are shown in Table 10.

[0108]

Table 10

[0109] In the anti-influenza virus test, Coating film 2 using the composition (AgZn-TAZ) obtained in Example 3 showed good antiviral activity even after the water resistance operation.

[0110] Anti-influenza virus test (with light resistance operation) Coating film 2 and Coating film 3 were each irradiated with light under the following apparatus, light source, and conditions (hereinafter, light resistance operation), and then the test was conducted in the same manner as the anti-influenza virus test. Apparatus: Xenon light resistance tester ATLAS Suntest XLS+ Light source: Xenon Condition: Irradiance: 60 W / m2 (300 - 400 nm) Blackboard temperature (black standard): 63 °C Treatment time: 10 hours

[0111] The results of the anti-influenza virus test (with light resistance operation) are shown in Table 11.

[0112]

Table 11

[0113] In the anti-influenza virus test, Coating Film 2 using the composition (AgZn-TAZ) obtained in Example 3 showed good antiviral activity even after the light resistance operation.

[0114] Anti-feline calicivirus test Under the following conditions, in accordance with ISO 21702, an anti-feline calicivirus test was conducted using Coating Film 2 and Coating Film 3. Virus: Feline calicivirus F-9 strain (Feline calicivirus, ATCC VR-782) Host: CRFK cells (ATCC CCL-94) Inoculation: Test virus solution concentration 1.3×10 7 pfu / ml, inoculation volume 0.4 ml Action conditions: Dark place, 25 °C, 0 hours and 24 hours Virus infectivity titer measurement method: Plaque method

[0115] The results of the anti-feline calicivirus test are shown in Table 12.

[0116]

Table 12

[0117] In the anti-feline calicivirus test, Coating Film 2 using the composition (AgZn-TAZ) obtained in Example 3 showed good antiviral activity.

[0118] Feline calicivirus test (with water resistance operation) After subjecting Coating Film 2 and Coating Film 3 to the water resistance operation respectively, tests were conducted in the same manner as the above feline calicivirus test. The results of the feline calicivirus test (with water resistance operation) are shown in Table 13.

[0119]

Table 13

[0120] In the feline calicivirus test, Coating Film 2 using the composition (AgZn-TAZ) obtained in Example 3 showed good antiviral activity even after the water resistance operation.

[0121] Feline calicivirus test (with light resistance operation) After subjecting Coating Film 2 and Coating Film 3 to the light resistance operation respectively, tests were conducted in the same manner as the above feline calicivirus test. The results of the feline calicivirus test (with light resistance operation) are shown in Table 14.

[0122]

Table 14

[0123] In the feline calicivirus test, Coating Film 2 using the composition (AgZn-TAZ) obtained in Example 3 showed good antiviral activity even after the light resistance operation.

Industrial Applicability

[0124] The pest control composition of the present invention is excellent in pest control activity, with suppressed coloring, reduced color tone change due to environmental factors, etc., and can be widely used for pest control applications such as anti-corrosion, anti-mold, antibacterial, disinfection, antiviral, and anti-algae.

Claims

Claim 1 (A) A nitrogen-containing heterocyclic compound represented by formula (1) and / or a salt thereof, 【Chemical 1】 (In formula (1), X is a nitrogen atom or a substituted or unsubstituted carbon atom, Y is a nitrogen atom or a substituted or unsubstituted carbon atom, and Z is a substituted or unsubstituted carbon atom. When Y is a carbon atom, Y and Z may together form a substituted or unsubstituted benzene ring or a substituted or unsubstituted 6-membered heterocycle.) (B) One or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper, and (C) A silver component A pest control composition containing a complex containing these. Claim 2 The pest control composition according to claim 1, wherein the molar ratio of the nitrogen-containing heterocyclic compound represented by formula (1) to one or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper and the silver component is 10:1 to 1:

4. Claim 3 The pest control composition according to claim 1 or 2, wherein the content ratio of the silver component is equimolar or more with respect to one or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper. Claim 4 The pest control composition according to any one of claims 1 to 3, wherein the nitrogen-containing heterocyclic compound represented by formula (1) is any one of 1,2,4-triazole, methyltetrazole, benzotriazole, xanthine, hypoxanthine, and methylbenzotriazole. Claim 5 The pest control composition according to any one of claims 1 to 4, wherein one or more metal components selected from the group consisting of aluminum, calcium, magnesium, zinc, and copper is a zinc component. Claim 6 A resin molded article containing the pest control composition according to any one of claims 1 to 5. Claim 7 A paint containing the pest control composition according to any one of claims 1 to 5. Claim 8 A pest control composition containing at least one of the pest control composition according to any one of claims 1 to 5 and other industrial biocides.

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