Coordination polymer and pest control composition containing the same

Abstract

The present invention addresses the problem of providing a thiabendazole-containing composition for pest control which is reduced in color tone change due to light or heat, is less apt to decompose at high temperatures, and is inhibited from dissolving in water.　This pest control composition contains a coordination polymer comprising thiabendazole (TBZ), terephthalic acid (BDC), and zinc (Zn). The coordination polymer is represented by formula (I) [Zna(TBZ)b(BDC)cRd]n, the constituent units having been linked to one another by coordination bonds. In formula (I), R represents a counter ion for a zinc ion; a, b, and c are each an integer of 1 or larger; d is an integer of 0 or larger; and n is the number of linked constituent units represented by Zna(TBZ)b(BDC)cRd and is not particularly limited.　The coordination polymer may be a solvent adduct.

Description

Technical Field

[0001] The present invention relates to a coordination polymer containing thiabendazole. Specifically, it relates to a coordination polymer containing thiabendazole, terephthalic acid and zinc, and a pest control composition containing the same. This application claims priority to Japanese Patent Application No. 2020-196167 filed on November 26, 2020, the content of which is incorporated herein by reference.

Background Art

[0002] Thiabendazole is widely used as a fungicide, mold inhibitor, preservative, anthelmintic, etc. For example, Patent Documents 1 to 4 describe that thiabendazole is used for wood products, paper, PVC, etc. for these purposes. Thiabendazole itself has a certain degree of stability, but it undergoes decomposition and coloring by light (ultraviolet rays) and decomposition by heat (disappears at high temperatures). By complexing with various substances, such decomposition and disappearance can be suppressed, that is, the physical stability can be improved. However, the complex itself may be colored, or even if the complex itself is white, it may be colored by light or heat. As a result, when used as a composition, there is a problem that the color and texture of the material to be mixed are lost. On the other hand, coordination polymer compounds composed of thiabendazole, polyvalent carboxylic acid and heavy metal ions are described in Non-Patent Documents 1 and 2. However, although these documents describe the crystal structure, there is no description indicating that the polyvalent carboxylic acid is terephthalic acid, that the change in color tone due to light or heat is reduced, and that it is difficult to decompose even when heated to a high temperature. There is also no description about excellent weather resistance and being preferably used for biocide applications.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Non-Patent Document

[0004]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a pest control composition containing thiabendazole, which has reduced color tone change due to light or heat, is difficult to decompose even when heated at a high temperature, and has suppressed water elution.

Means for Solving the Problems

[0006] As a result of repeated studies to achieve the above object, the present inventors have found that a pest control composition containing thiabendazole, which is difficult to decompose even when heated at a high temperature, can be provided by using a coordination polymer containing thiabendazole, terephthalic acid and zinc, and have completed the present invention.

[0007] That is, the present invention includes the following aspects. (1) A coordination polymer containing thiabendazole (TBZ), terephthalic acid (BDC) and zinc (Zn). (2) Formula (I) [Zna (TBZ) b (BDC) c R d n (I) (wherein R represents a counter anion of zinc ion; a, b, and c represent integers of 1 or more, and d represents an integer of 0 or more; n represents the number of sets of structural units represented by Zn a (TBZ) b (BDC) c R d which is the number of sets of structural units represented by, and is not particularly limited) The coordination polymer according to (1), which is a compound represented by or a solvate thereof. (3) [Zn(TBZ)(BDC)]n or [Zn 4 (TBZ) 2 (BDC) 3 n (in these formulas, n is the number of sets of structural units represented by Zn(TBZ)(BDC) or Zn 4 (TBZ) 2 (BDC) 3 which is not particularly limited), and represents the coordination polymer according to (1) or (2). (4) A pest control composition containing the coordination polymer according to any one of (1) to (3). (5) The pest control composition according to (4), which further contains any one of an antimicrobial component, an insecticide, a herbicide, and a plant growth regulator. (6) The pest control composition according to (4) or (5), which is used as a microbial contamination control agent for industrial products. (7) The pest control composition according to (6), wherein the pest control composition is a resin composition. (8) The pest control composition according to (6), wherein the pest control composition is a fiber or a thread. [Advantages of the Invention]

[0008] The thiabendazole-containing coordination polymer according to the present invention is less likely to cause a change in color tone due to light or heat, is less likely to decompose even when heated at a high temperature, and is less likely to elute into water. Therefore, it is particularly useful for use in outdoor scenes where light is applied, fields where high heat is applied, and scenes where there are many opportunities to come into contact with water. ​

Brief Description of the Drawings

[0009]

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Modes for Carrying Out the Invention

[0010] The pest control composition of the present invention contains a coordination polymer containing thiabendazole, terephthalic acid and zinc.

[0011] (1) Coordination polymer containing thiabendazole A coordination polymer containing thiabendazole, terephthalic acid and zinc (hereinafter referred to as "thiabendazole-containing coordination polymer") may have different polymer structures depending on the zinc species, but all of them are excellent as a pest control composition. A coordination polymer is a complex having a continuous structure composed of a polydentate ligand and a metal ion. For example, from a bidentate ligand L and a divalent metal ion M, a coordination polymer with a (-M-L-M-L-) structure connected in series can be generated. In a coordination polymer, the metal ion is located in the main chain. In the case of the present invention, coordination polymers with different dimensional structures can be obtained depending on the type of zinc salt, but the structure of the coordination polymer is not particularly limited. Any structure can reduce the color change due to light or heat, is difficult to decompose even when heated at a high temperature, and a pest control composition containing thiabendazole with suppressed water elution can be obtained.

[0012] The coordination polymer of the present invention has the following formula (I) [Zn a (TBZ) b (BDC) c R d n (I) and is represented by Zn a (TBZ) b (BDC) c R d Each structural unit represented by is connected by a coordination bond. It may also be a solvate in which a solvent is incorporated into the coordination polymer. In formula (I), TBZ represents thiabendazole, BDC represents terephthalic acid, and R represents a counter anion of a zinc ion. The counter anion is the anion part of the zinc compound, and examples include halogeno anions such as F, Cl, Br or I; inorganic anions such as NO 3 , SO 4 ; and organic anions such as HCOO, CH 3 COO, acac. a, b and c each independently represent an integer of 1 or more, specifically, an integer in any range of 1 to 50, 1 to 10, 1 to 5, etc., and d represents an integer of 0 or more, specifically, an integer in any range of 0 to 50, 0 to 10, 0 to 5, etc. n is Zn a (TBZ)​b (BDC) c R d is the number of sets of structural units, and is not particularly limited as long as the effects of the present invention can be achieved.

[0013] Specifically, as shown in the examples, the structural units are Zn(TBZ)(BDC), Zn 4 (TBZ) 2 (BDC) 3 ·6DMF and other coordination polymers can be mentioned. Here, DMF represents N,N-dimethylformamide which is a solvent. For example, in the case of a coordination polymer in which the structural unit is Zn(TBZ)(BDC) as shown by the molecular model in FIG. 2, in each structural unit, one Zn ion (Zn1: coordination number 6) in which two N atoms in one molecule of TBZ and two O atoms of one COOH group in two molecules of BDC coordinate, and in each structural unit, two O atoms of one COOH group in BDC coordinate to Zn ions (Zn1) of other structural units, thereby connecting linearly. Also, in the case of a coordination polymer in which the structural unit is Zn 4 (TBZ) 2 (BDC) 3 ·6DMF, the four zinc ions in each structural unit have two zinc ions (Zn1: coordination number 4) in which one N atom in one molecule of TBZ and one O atom in one COOH group in three molecules of BDC coordinate, and two zinc ions (Zn2: coordination number 5) in which the remaining two N atoms in one molecule of TBZ and one O atom in one COOH group in three molecules of BDC coordinate. Each structural unit is connected in a network form by the coordination of N atoms in TBZ and O atoms in BDC to zinc ions (Zn1 and Zn2) of other structural units, and as a result, one-dimensional channel pores are formed. And six DMFs which are solvents are incorporated in each structural unit.

[0014] (Thiabendazole: TBZ) Thiabendazole is a compound represented by the following formula and is a well-known compound as a fungicide or the like.

Chemical formula

[0015] (Terephthalic acid: BDC) Terephthalic acid is a compound represented by the following formula. [Chemical formula]

[0016] (Zinc salt) The zinc salt is a divalent inorganic or organic zinc salt. Examples of the inorganic salts include salts of inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and halides such as chlorides, bromides, and iodides. Examples of the organic salts include salts of organic acids such as formic acid, acetic acid, lactic acid, oxalic acid, citric acid, succinic acid, malic acid, and benzoic acid. Among these, nitrates, acetates, sulfates, chlorides, bromides, iodides, and lactates are preferred. These zinc salts may be used alone or in combination of two or more.

[0017] (Solvent) The solvent used in the synthesis is not particularly limited, but an organic solvent, water, or a mixed solvent thereof can be used. The solvent can be used alone or as a mixed solvent of two or more. The organic solvent is not particularly limited, but specifically includes alcohol compounds such as methanol, ethanol, and propanol; ether compounds such as diethyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as methylene chloride and chloroform; acetone, ethyl acetate, acetonitrile, N,N-dimethylformamide (DMF), N,N-diethylformamide, N,N-dimethylacetamide, etc. Among these, it is preferable to use N,N-dimethylformamide. These solvents may remain in the coordination polymer as long as the purpose of pest control is not inhibited.

[0018] (2) Preparation of Thiabendazole-Containing Coordination Polymer In a solvent, a thiabendazole-containing coordination polymer can be obtained by mixing thiabendazole, terephthalic acid, and a zinc salt. The conditions during mixing are as follows.

[0019] The mixing ratio of the zinc salt to terephthalic acid is preferably in the molar ratio range of zinc salt:terephthalic acid = 1:5 to 5:1, and more preferably in the range of 1:1 to 4:1. The mixing ratio of the zinc salt to thiabendazole is preferably in the molar ratio range of zinc salt:thiabendazole = 1:5 to 5:1, and more preferably in the range of 1:2 to 2:1.

[0020] When carrying out the reaction in a solvent, the molar concentration of the zinc salt in the solvent is preferably 0.005 - 5 mol / L, and more preferably 0.01 - 2 mol / L. The molar concentration of terephthalic acid is preferably 0.001 - 5 mol / L, and more preferably 0.005 - 2 mol / L. The molar concentration of thiabendazole is preferably 0.001 - 5 mol / L, and more preferably 0.005 - 2 mol / L.

[0021] The thiabendazole-containing coordination polymer may be obtained simply by mixing the zinc salt, terephthalic acid, and thiabendazole, or it may 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 coordination polymer showing the above-mentioned predetermined characteristics is obtained, but the range of room temperature to 200 °C is preferred. When heating, it is preferably 100 - 150 °C.

[0022] The reaction time of this production method is not particularly limited as long as a coordination polymer showing the above-mentioned predetermined characteristics is obtained, but in terms of better yield of the product, it is preferably 1 hour or more, and more preferably 24 hours or more. At room temperature, it is preferably 24 hours or more, and the heating time in the heating step is preferably 6 hours or more.

[0023] The procedure of this manufacturing method is not particularly limited as long as a coordination polymer exhibiting the above-mentioned predetermined characteristics is obtained. For example, a method of mixing thiabendazole, terephthalic acid, and a zinc salt in the presence of a solvent and heating them is preferably 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 completion of the reaction, 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, etc., or separation means combining these. Preferably, after filtration, it is washed well with a solvent in which raw material terephthalic acid and zinc salt dissolve, and vacuum dried at 100 °C to 150 °C. As this solvent, for example, the same solvent as used in the above synthesis can be used.

[0025] The structure, composition, and performance of the product can be confirmed using general methods. For example, X-ray diffraction measurement (confirmation of crystal structure), 13C-CPMAS-NMR measurement (composition analysis of the product), thermal analysis (measurement of heat resistance), etc. can be used. X-ray diffraction measurement and 13C-CPMAS-NMR are measured at room temperature with the powder as it is, and thermal analysis is measured by heating the powder in air from room temperature to 1000 °C.

[0026] (3) Optional components The pest control composition of the present invention may contain only the above components, but may also contain the following components.

[0027] (A) Resin As the resin contained in the pest control composition of the present invention, various resins can be used according to the use of the pest control composition, required performance, etc. Examples of the resin include thermoplastic resins and thermosetting or photocurable resins. These may be used alone or in combination of two or more.

[0028] a) Thermoplastic resin The thermoplastic resin used in the present invention is not particularly limited. Specifically, it includes styrene resins, acrylic resins, vinyl acetate resins, acrylonitrile copolymers, polyphenylene oxide resins (PPO), polysulfone resins (PSF, PSU), polyethersulfone (PES), polyarylate (PAR), polyetherimide (PEI), polyamideimide (PAI), polyimide (PI), polymethyl methacrylate, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-N-substituted maleimide terpolymer, acrylonitrile-butadiene-styrene copolymer (ABS resin), styrene-maleic anhydride copolymer, styrene-maleic anhydride-N-substituted maleimide terpolymer, polycarbonate resin (PC), polybutylene terephthalate resin (PBT), LLDPE (linear low density polyethylene), LDPE (low density polyethylene), HDPE (high density polyethylene), polyethylene terephthalate resin (PET), polyvinyl chloride (PVC), polyethylene, polypropylene, artificial thermoplastic polyolefin (TPO), styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), hydrogenated SBS, styrene-isoprene-styrene (SIS), various olefin-based elastomers, various polyester-based elastomers, polystyrene (PS), methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate copolymer, polyacetal resin (POM), modified polyphenylene ether resin (modified PPE), ethylene-vinyl acetate copolymer (EVA), polyphenylene sulfide resin (PPS), polyethersulfone resin (PES, PESU), polyphenylsulfone (PPSU), polyether ketone (PEK), polyether ether ketone resin (PEEK), polyether, polyacrylate, liquid crystal polyester resin, liquid crystal polymer (LCP), polyamide resin (nylon), fluororesin, polyvinyl pyrrolidone (PVP), etc.

[0029] b) Thermosetting or photocurable resin Although the thermosetting or photocurable resin used in the present invention is not particularly limited, monomers, prepolymers, oligomers, polymers, etc. having a vinyl group, (meth)acryloyl group, epoxy group, or oxetanyl group can be used. Among them, it is preferable to use a polyfunctional resin. In the present invention, the "(meth)acryloyl group" means an "acryloyl group" and / or a "methacryloyl group".

[0030] As the above thermosetting or photocurable resin, specifically, a polyfunctional or monofunctional (meth)acrylate monomer or acrylate oligomer can be used. Among them, it is preferable to contain a polyfunctional acrylate having two or more polymerizable unsaturated groups.

[0031] The above monofunctional acrylate monomer is a monomer having one (meth)acrylate group in the molecule, and examples thereof include tricyclodecane acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, and phenoxyethyl acrylate. In the present invention, the "(meth)acrylate group" means an "acrylate group" and / or a "methacrylate group".

[0032] In addition, the above polyfunctional acrylate monomer is a monomer having two or more, preferably 2 to 6, (meth)acrylate groups in the molecule, and examples thereof include tricyclodecane dimethylol diacrylate, neopentyl glycol diacrylate, neopentyl glycol hydroxypivalate diacrylate, dioxane glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, bisphenol A type polyethoxylate diacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0033] Examples of the acrylate oligomer include epoxy acrylate oligomer, polyester polyacrylate oligomer, urethane acrylate oligomer, and the like.

[0034] These polyfunctional or monofunctional (meth)acrylate monomers or oligomers can be used alone or in combination of two or more.

[0035] Specific examples include silicone resin, silicone resin, acrylic silicone resin, epoxy resin, polyurethane, phenolic resin, melamine resin, urea resin, unsaturated polyester resin, silicone resin, diallyl phthalate resin, and the like.

[0036] (B) Solvent The pest control composition of the present invention may contain a solvent capable of dispersing or dissolving a coordination polymer composed of thiabendazole, terephthalic acid and zinc, or a mixture of the coordination polymer and a resin or the like. The solvent is not particularly limited, but examples include 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, and the like. These solvents may be used alone or in combination of two or more.

[0037] (C) Others In the pest control composition of the present invention, various other components can be added according to the purpose, as long as the effects of the present invention are not impaired. Such components include flame retardants, heat stabilizers, antioxidants, lubricants, antistatic agents, ultraviolet absorbers, colorants, mold release agents, heat insulating agents, dispersants, surfactants, pH adjusters, defoamers, rust preventives, viscosity modifiers, sequestering agents, friction modifiers, other antibacterial components, bactericidal components, antiviral components, antifungal components, preservative components and other components having antimicrobial properties, insecticides, herbicides, plant growth regulators and the like. Two or more of these can be used in combination.

[0038] (Flame retardant) The flame retardant is not particularly limited. For example, halogen-based flame retardants such as chlorine-based and bromine-based flame retardants; organic flame retardants such as phosphorus-based flame retardants; inorganic flame retardants such as nitrogen-containing flame retardants, antimony-based flame retardants, metal hydroxide-based flame retardants, boron-based flame retardants (boric acid flame retardants), and red phosphorus-based flame retardants can be used. Two or more of these can be used in combination.

[0039] (Heat stabilizer) The heat stabilizer is not particularly limited. For example, phosphorus-based heat stabilizers such as phosphite esters and phosphate esters can be mentioned. Examples of phosphites include triesters, diesters, and monoesters of phosphorous acid such as triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyldiphenyl phosphite, monooctyldiphenyl phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis[(4,6-di-tert-butylphenyl) octyl phosphite], etc. Examples of phosphates include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, tetrakis(2,4-di-tert-butylphenyl)-4,4-diphenylene phosphonite, etc.

[0040] (Antioxidant) The antioxidant is not particularly limited, and examples thereof include phenolic antioxidants, phosphorus-based antioxidants, phosphite-based antioxidants, thiourea-based antioxidants, etc.

[0041] (Lubricant) The lubricant is not particularly limited, and examples thereof include higher fatty acids, ester waxes, polyethylene waxes, metal soaps, etc.

[0042] (Antistatic agent) The antistatic agent is not particularly limited, and examples thereof include fatty acid amines, fatty alcohols, fatty acid esters, fatty acid amides, sulfonic acid compounds, etc.

[0043] (Ultraviolet inhibitor) The ultraviolet inhibitor is not particularly limited. For example, it includes salicylic acid derivative compounds, benzophenone compounds, benzotriazole-based compounds such as benzotriazole derivatives, and cyanoacrylate compounds.

[0044] (Colorant) The colorant is not particularly limited. For example, it includes organic pigments, inorganic pigments, dyes, brighteners, etc. Examples of organic pigments include phthalocyanine-based, benzimidazolone-based, azo-based, azomethine azo-based, azomethine-based, anthraquinone-based, perinone·perylene-based, indigo·thioindigo-based, dioxazine-based, quinacridone-based, isoindoline-based, isoindolinone-based pigments, and carbon black pigments. Examples of inorganic pigments include extender pigments, titanium oxide-based pigments, iron oxide-based pigments, spinel pigments, etc. More specifically, insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow, pyrazolone red, soluble azo pigments such as lithol red, heliobordeaux, pigment scarlet, permanent red 2B, phthalocyanine-based such as phthalocyanine blue, phthalocyanine green, quinacridone-based such as quinacridone red, quinacridone magenta, perylene-based such as perylene red, perylene scarlet, isoindolinone-based such as isoindolinone yellow, isoindolinone orange, pyranthrone-based such as pyranthrone red, pyranthrone orange, thioindigo-based, condensed azo-based, benzimidazolone-based, quinophthalone yellow, nickel azo yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine violet and other conventionally known pigments can be used. As dyes, for example, conventionally known dyes such as direct dyes, basic dyes, cationic dyes, acidic dyes, mordant dyes, acid mordant dyes, sulfur dyes, naphthol dyes, disperse dyes, reactive dyes can be used. Examples of brighteners include aluminum paste, mica, flaky iron oxide, etc.

[0045] (Release agent) The release agent is not particularly limited, and examples thereof include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000, polysiloxane-based silicone oils, and the like. Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acids. Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetratetracontanoic acid, montanic acid, adipic acid, azelaic acid, and the like. As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same ones as the above aliphatic carboxylic acids can be used. Examples of the alcohol that reacts with this aliphatic carboxylic acid to form an ester include saturated or unsaturated monohydric alcohols, saturated or unsaturated polyhydric alcohols, and the like. Here, aliphatic includes alicyclic compounds. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. These ester compounds of aliphatic carboxylic acids and alcohols may contain aliphatic carboxylic acids and / or alcohols as impurities, or may be a mixture of a plurality of compounds.

[0046] Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture mainly composed of myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate. Examples of aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, micro wax, polyethylene wax, Fischer-Tropsch wax, or α-olefin oligomers having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbons include alicyclic hydrocarbons. Further, these hydrocarbon compounds may be partially oxidized. Examples of polysiloxane-based silicone oils include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, fluorinated alkyl silicone, etc. These may be used alone or in combination of two or more.

[0047] (Heat insulating agent) The heat insulating agent is not particularly limited as long as it is generally used by those skilled in the art, such as infrared (near-infrared) shielding agents, absorbing pigments, and reflective pigments (heat insulating pigments).

[0048] (Dispersant) A dispersant is an additive used to uniformly disperse solid particles such as inorganic and organic pigments in a medium to prepare a stable dispersion. It is not particularly limited as long as the purpose of particle dispersion can be achieved, and for example, various surfactants can be used.

[0049] (Surfactant) Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Examples of nonionic surfactants include polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene aryl phenyl ethers, polyoxyalkylene alkyl ethers, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene vegetable oils, and the like. Examples of anionic surfactants include alkylbenzene sulfonates, alkylnaphthalene sulfonates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, dialkyl sulfosuccinates, and the like. Examples of cationic surfactants include aliphatic amine salts, quaternary ammonium salts, and the like. Examples of amphoteric surfactants include alkyl betaine type surfactants, amidopropyl betaine type surfactants, imidazolinium betaine type surfactants, sulfobetaine type surfactants, phosphobetaine type surfactants, and the like. These surfactants can be used alone or in combination of two or more.

[0050] (pH adjuster) The pH adjuster is not particularly limited, and examples thereof include organic acids such as succinic acid, citric acid, tartaric acid, and acetic acid and their salts, inorganic acids such as phosphoric acid, polyphosphoric acid, and boric acid and their salts, and the like.

[0051] (Defoaming agent) The defoaming agent is not particularly limited, and examples thereof include defoaming agents such as mineral oil-based, silicone-based, polyether-based, fluoroalkyl ether, polyalkylene glycol-based, and the like.

[0052] (Rust inhibitor) The rust inhibitor is not particularly limited. For example, it includes metal sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, organic phosphite esters, organic phosphate esters, metal salts of organic sulfonic acids, metal salts of organic phosphates, alkenyl succinic acid esters, polyhydric alcohol esters, benzotriazole-based compounds, etc.

[0053] (Viscosity modifier) The viscosity modifier is not particularly limited. For example, it includes xanthan gum, carboxymethyl cellulose, hydroxyethyl cellulose, gum arabic, gellan gum, pullulan, etc.

[0054] (Metal sequestering agent) The metal sequestering agent is not particularly limited. For example, it includes ethylenediaminetetraacetic acid or its salts, nitrilotriacetic acid or its salts, diethylenetriaminepentaacetic acid or its salts, hydroxyethylethylenediaminetriacetic acid or its salts, triethylenetetraminehexaacetic acid or its salts, 1,3-propanediaminetetraacetic acid or its salts, 1,3-diamino-2-hydroxypropane tetraacetic acid or its salts, 1-hydroxyethylidene-1,1-diphosphonic acid or its salts, hydroxyethyliminodiacetic acid or its salts, dihydroxyethylglycine or its salts, glycol ether diamine tetraacetic acid or its salts, dicarboxymethylglutamic acid or its salts, nitrilotris(methylenephosphonic acid) or its salts, etc.

[0055] (Friction modifier) The friction modifier is not particularly limited. For example, it includes fatty acids, fatty acid esters, alcohols, etc.

[0056] (Components having antimicrobial properties such as other antibacterial components, bactericidal components, antiviral components, antifungal components, preservative components, etc.) As components having antimicrobial properties such as other antibacterial components, bactericidal components, antiviral components, antifungal components, preservative components, etc., they can be used without particular limitation. The active components to be used may be liquid or solid, may be organic compounds or inorganic compounds, and may be single compounds or mixtures. These can be used by mixing them in any ratio, and one component or a combination of multiple types of components can be used.

[0057] Specific examples are shown below. As antibacterial components, bactericidal components, antiviral components, antifungal components, preservative components, etc., there are benzimidazole-based compounds such as benomyl, carbendazim, thiabendazole, and thiophanate-methyl; phenylcarbamate-based compounds such as diethofencarb; dicarboximide-based compounds such as procymidone, iprodione, and vinclozolin; azole-based compounds such as triflumizole, hexaconazole, diniconazole, epoxyconazole, tebuconazole, difenoconazole, cyproconazole, propiconazole, flusilazole, triadimefon, metconazole, microbutanil, imazalil, and trifolin; acylalanine-based compounds such as metalaxyl; carboxamide-based compounds such as flutolanil, mepronil, flutolanil, and triflumizamide; organophosphorus-based compounds such as tolclofos-methyl, fosetyl-aluminum, and pyrazophos; anilinopyrimidine-based compounds such as pyrimethanil, mepanipyrim, and cyprodinil; cyanopyrrole-based compounds such as fluazinam and fenpiclonil; antibiotics such as blasticidin S, kasugamycin, polyoxin, and validamycin; methoxyacrylate-based 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-propylbutylcarbamate, 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,Quaternary ammonium salt-based compounds such as N-dimethylammonium carbonate, biguanide-based compounds such as polyhexamethylene biguanide (PHMB), polyhexamethylene guanidine (PHMG), chlorhexidine gluconate, pyridinium-based compounds such as cetylpyridinium chloride, dodecylpyridinium chloride, organic iodine-based compounds such as 3-iodo-2-propynyl-butylcarbamate (IPBC), pyridine-based compounds such as 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine (TCMSP), pyrithione-based compounds such as zinc pyrithione, sodium pyrithione, benzothiazole-based compounds such as 2-(4-thiocyanomethylthio)benzothiazole, imidazole-based compounds such as methyl-2-benzimidazolecarbamate, 2-(4-thiazolyl)-benzimidazole, thiocarbamate-based compounds such as tetramethylthiuram disulfide, nitrile-based compounds such as 2,4,5,6-tetrachloroisophthalonitrile, haloalkylthio-based compounds such as N-(fluorodichloromethylthio)-phthalimide, N-(fluorodichloromethylthio)-N,N’-dimethyl-N-phenyl-sulfamide, triazole-based compounds such as α-t-butyl-α(p-chlorophenylethyl)-1H-1,2,4-triazole-1-ethanol (common name tebuconazole), 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, 4,5-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,Isothiazoline compounds such as 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), dimethoate, metobenzuron, cumyluron, nicosulfuron, linuron, cypriotrin, terbutryn, simazine, atrazine, propazine, cyanazine, dimethamethrin, promethrin, butralin, benfluralin, pro-diamine, benzofenap, pyraflufen-ethyl, biphenox, bromobutide, bromoxynil, propanil, diflufenican, mefenacet, chlormepropp, 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.,

[0058] (Insecticides, herbicides, plant growth regulators, etc.) The pest control composition of the present invention can also be used as a composition together with insecticides, herbicides, plant growth regulators, 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. These can be mixed and used in any ratio, and one component or a combination of multiple components can be used., Specific examples are shown below., As insecticides, 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, phosalone, 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;Fipronil, cartap, buprofezin, thicyclam, bensultap, phenoxycarb, phenothrin, fenpyroximate, pyridaben, pyriproxyfen, hydramethylnon, thiodicarb, phenobucarb, chlorfenapyr, fenproximate, pymetrozine, pyrimidifen, tebufenozide, tebufenpyrad, methoxyfenozide, thiazamate, indoxacarb, sulfraflamide, milbemectin, abamectin, chlorantraniliprole, pyriprole, broflanilide, flupyradifurone, dichloromethothiaz, boric acid, disodium octaborate tetrahydrate, borax, borax pentahydrate, paradichlorobenzene, capric acid, etc. can be mentioned.;

[0059] As herbicides, 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, acifluorfen Na salt, sulfentrazone, paraquat, flumeturon, triflusulfuron-methyl, fenoxaprop-p-ethyl, cyhalofop-butyl, diflufenican, norflurazon, isoxaflutole, glufosinate ammonium salt, glyphosate, bentazone, benthiocarb, mefenacet, propanil, fluthiamide, etc. can be mentioned.

[0060] Examples of plant growth regulators include maleic hydrazide, chlormequat, 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.

[0061] (Polymerization initiator) When a thermosetting or photocuring resin is used as the resin, it may contain a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator.

[0062] Examples of the photopolymerization initiator that can be used in the present invention include acetophenone-based initiators such as 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [Darocur 2959: manufactured by Merck], α-hydroxy-α,α'-dimethylacetophenone [Darocur 1173: manufactured by Merck], methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651]; benzoin ether-based initiators such as benzoin ethyl ether, benzoin isopropyl ether; and other examples include halogenated ketones, acylphosphine oxides, acylphosphonates, and the like.

[0063] The thermal polymerization initiators that can be used in the present invention include azo-based initiators and peroxide-based initiators.

[0064] Examples of azo initiators include azobis(isobutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[2-(hydroxymethyl)propionitrile], 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyric acid dimethyl), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, etc. Among these, azobis(isobutyronitrile) is preferred in terms of cost and versatility.

[0065] As the peroxide initiator, those with a relatively easy decomposition and a half-life temperature of 80°C or lower for 10 hours are preferred. Examples include benzoyl peroxide, isobutyryl peroxide, cumyl peroxyoctoate, etc. As the peroxide initiator, those with a short thermal polymerization time and stable as the reactive composition before polymerization can be appropriately selected.

[0066] Such polymerization initiators are compounded in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total curable resin.

[0067] (4) Method for producing the pest control composition The pest control composition of the present invention can be used as it is by preparing a thiabendazole-containing coordination polymer. If necessary, after preparing the thiabendazole-containing coordination polymer, it is mixed with other components such as resins. The mixing method can be carried out by a conventionally known method. For example, when using a resin, it can be produced by melt-kneading. Specifically, a predetermined amount of a thermoplastic resin, a thiabendazole-containing coordination polymer, and other additive components blended as required 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.

[0068] The pest control composition containing the resin according to the present invention is mainly used as a resin material for manufacturing (molding) various products (molded articles). As the molding method, 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 an adiabatic mold, molding methods using a rapid heating 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.

[0069] The mixing amount of the thiabendazole-containing coordination polymer in the pest control composition of the present invention is not particularly limited. It can be appropriately changed depending on what is to be mixed.

[0070] When using a resin, the mixing amount of the resin is not particularly limited, but preferably it is 1 to 1000 parts by weight, preferably 1 to 300 parts by weight, based on 1 part by weight of the thiabendazole-containing coordination polymer.

[0071] When using a solvent, the mixing amount of the solvent is not particularly limited, but preferably it is 1 to 1000 parts by weight, preferably 2 to 100 parts by weight, based on 1 part by weight of the thiabendazole-containing coordination polymer.

[0072] The pest control composition containing the resin according to the present invention and its molded article exhibit antimicrobial activities such as antibacterial activity, antifungal activity, and antiviral activity. Therefore, it can be preferably used for applications requiring antimicrobial properties, such as 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, sealants, adhesives, paints; exterior building materials such as resin siding, ceramic siding, tiles; absorbent fiber products such as diapers, napkins, incontinence pads, and medical and health 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, eye drop containers, contact lenses, spectacle lenses, intraocular lenses, dental and medical materials such as oral treatment tools, bedding, socks, underwear and other textile products; housing members such as the outer packaging materials of personal computers and the outer packaging materials of 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.

[0073] In addition, the pest control composition of the present invention can also be preferably used as a composition with at least one selected from paints, pigments, inks, fibers, pulp, rubbers, latexes, adhesives, films, formulations, ceramic materials, and metalworking oils. Examples of the fibers include natural fibers {plant fibers such as cotton and hemp; animal fibers such as silk, wool, rabbit hair, alpaca, and feathers; mineral fibers such as asbestos}, Chemical fibers {synthetic fibers (polyamide-based such as nylon and aramid fibers; polyvinyl alcohol-based such as vinylon; polyvinylidene chloride-based such as vinylidene; polyvinyl chloride-based such as polyvinyl chloride; polyester-based such as polyester; polyacrylonitrile-based such as polyacrylonitrile fiber and modacrylic fiber; polyolefin-based such as polyethylene fiber, polypropylene fiber, and polystyrene fiber; polyurethane-based such as polyurethane; polychloral-based such as polychloral; polyfluoroethylene-based such as fluorine fiber; phenol-based such as novoloid; polyether ester-based such as Lex and Success; polylactic acid-based such as polylactic acid fiber; polyalkylene paraoxybenzoate-based such as benzoate; polytetrafluoroethylene-based; polyvinylidene cyanide-based; polyurea-based), regenerated fibers (cellulose-based such as rayon, viscose rayon, polynosic, cupra, tencel, and lyocell; cuprammonia-based such as cuprammonia rayon; protein-based such as casein fiber, vegetable protein fiber, and regenerated silk thread; algin fiber; chitin fiber; mannan fiber; rubber fiber) semi-synthetic fibers (cellulose-based such as acetate, triacetate, and oxidized acetate; protein-based such as promix; rubber chloride; hydrochloric acid rubber) inorganic fibers (glass fibers such as glass fiber; carbon fibers such as carbon fiber; metal fibers; ceramic fibers such as silica fiber and alumina fiber)} etc., can be particularly preferably used.

[0074] In the present invention, examples of the form of the target fiber product include yarns, strings, ropes, fabrics (woven fabrics, knitted fabrics, non-woven fabrics), etc. Specific examples include linen products such as sheets, pillowcases, and towels; various clothing items such as pajamas, white coats, aprons, hats, uniforms, and work clothes; fashion accessories such as bags and shoes; seat sheets for seats such as car seats, chairs, and strollers and their seat covers; interior materials such as curtains and wallpapers; filters such as air conditioner filters and vacuum cleaner filters; outdoor supplies such as tents and sleeping bags; sanitary products such as masks; and can be widely used in household items and industrial materials such as refrigerator interior sheets and refrigerator covers.

[0075] The pest control composition according to the present invention exhibits antimicrobial activities such as antibacterial activity, antifungal activity, and antiviral activity. Therefore, it can be suitably used for various materials that require antimicrobial properties.

[0076] Examples are shown below, but the technical scope of the present invention is not limited thereto.

Example

[0077] Example 1: [Zn(TBZ)(BDC)] n coordination polymer of (hereinafter simply referred to as "Zn(TBZ)(BDC)") A suspension of thiabendazole: TBZ (0.403 g, 2 mmol), terephthalic acid: BDC (0.332 g, 2 mmol), and zinc chloride (0.273 g, 2 mmol) in DMF (48 ml) was sealed in a 110 ml glass vial and allowed to stand at 130°C for 48 hours to effect the reaction. After the reaction, single crystals were obtained by slowly cooling from 130°C to room temperature over 50 hours. Regarding the obtained single crystals, when the powder X-ray diffraction pattern was measured using a measuring device Bruker D2PHASER with CuKα rays, in the powder X-ray measurement from 5° to 50°, a diffraction pattern as shown in FIG. 1 was exhibited. (Powder X-ray diffraction pattern) 2θ (±0.2°) = 8.59, 9.01, 11.66, 12.83, 14.31, 15.03, 15.87, 16.17, 16.44, 17.14, 17.67, 18.06, 18.85, 19.03 20.47, 20.72, 21.09, 23.45, 24.32, 24.74, 25.45, 25.89, 26.44, 26.94, 27.22, 27.55, 27.90, 28.52, 29.53, 30.47, 30.86, 32.06, 32.32, 32.89, 33.19, 34.60, 35.50, 36.05, 36.59, 37.28, 37.49, 37.92, 38.20, 38.42, 39.10, 40.39, 41.01, 41.17, 42.31, 42.83, 43.60, 44.57, 45.19, 46.58, 46.58, 47.31, 48.01, 48.60, 48.98, 49.17

[0078] As a result of performing X-ray structure analysis on the single crystal obtained in Example 1, it was confirmed that it is a coordination polymer with a one-dimensional chain structure represented by Zn(TBZ)(BDC). The spatial information in the X-ray structure analysis is shown in Table 1, and the molecular model is shown in Figure 2.

[0079]

Table 1

[0080] (Other measurement results) Regarding the crystal obtained in Example 1, the measurement results by an infrared spectrophotometer (FT-IR) are shown in Figure 7. Also, regarding the crystal obtained in Example 1, the 13C-CPMAS-NMR measurement results are shown in Figure 8.

[0081] Example 2: [Zn 4 (TBZ) 2 (BDC) 3 ·6DMF] n The coordination polymer of (hereinafter simply referred to as "Zn 4 (TBZ) 2 (BDC)3 ·6DMF") The zinc chloride in Example 1 was changed to zinc nitrate hexahydrate (0.595 g, 2 mmol), and the reaction was carried out under the same conditions otherwise.

[0082] As a result of performing X-ray structure analysis on the single crystal obtained in Example 2, Zn 4 (TBZ) 2 (BDC) 3 It was confirmed that each structural unit represented by ·6DMF is connected in a network form and is a coordination polymer having one-dimensional channel pores. Zn 4 (TBZ) 2 (BDC) 3 ·6DMF means that 6 molecules of DMF per unit are incorporated into the pores. The spatial information in the X-ray structure analysis is shown in Table 2, and the molecular model is shown in Figure 3. 4 (TBZ) 2 (BDC) 3 It shows that 6 molecules of DMF per unit are incorporated into the pores. The spatial information in the X-ray structure analysis is shown in Table 2, and the molecular model is shown in Figure 3.

[0083]

Table 2

[0084] Thereafter, the sample Zn 4 (TBZ) 2 (BDC) 3 ·6DMF was allowed to stand in an environment of 150 °C and dried under reduced pressure with a vacuum pump to remove the solvent (DMF). For the single crystals before and after solvent removal, the powder X-ray diffraction pattern was measured using a CuKα ray with a measuring device Bruker D2PHASER. In the powder X-ray measurement from 5° to 50°, a diffraction pattern as shown in Figure 4 was shown. By removing the solvent, a slight difference was observed in the powder X-ray diffraction pattern. It was inferred that although a change in the interplanar spacing due to the elimination of lattice distortion etc. occurred before and after solvent removal, the influence on the skeleton was small. (Powder X-ray diffraction pattern) Zn 4 (TBZ) 2 (BDC)3 · 6DMF 2θ (±0.2°) = 5.49, 7.66, 8.63, 9.59, 10.78, 12.55, 13.21, 14.32, 15.11, 16.18, 16.53, 17.30, 17.77, 18.62, 19.04, 19.66, 21.64, 22.70, 24.02, 25.26, 26.09, 27.16, 28.70, 29.60, 32.56, 34.92, 35.82, 40.49, 44.08, 45.02 Zn 4 (TBZ) 2 (BDC) 3 2θ (±0.2°) = 5.76, 6.72, 8.83, 9.29, 9.65, 11.37, 13.35, 13.70, 14.08, 15.70, 17.11, 17.72, 18.56, 18.94, 20.08, 21.58, 22.76, 23.97, 26.28, 27.92, 28.61, 31.02, 32.55, 34.37, 35.93, 36.85, 40.42, 45.46, 47.61

[0085] (Thermal analysis) For the samples obtained in Examples 1 and 2 and TBZ (comparative example), after pulverization in an agate mortar, measurements were carried out using a TG-DSC (thermal analyzer) "METTLER TOLEDO TGA-DSC3+". The results are shown in Fig. 5. The weight loss accompanying the increase in heating temperature was shown to be significantly slower in both Examples 1 and 2 compared to the comparative example.

[0086] (Solubility test) 10 mg of the sample obtained in Example 1 was added to 50 mL of distilled water to make it saturated, and after stirring at room temperature for a certain time with a stir bar, it was filtered through a filter (0.2 um) and subjected to HPLC analysis to calculate the water solubility. As a result, the water solubility was 13.4 ppm for Zn(TBZ)(BDC), Zn 4 (TBZ) 2 (BDC) 3was 1.3 ppm, showing a significant decrease compared to 20.4 ppm of TBZ. The decreased solubility in water suppresses the elution amount of the active ingredient, especially in applications where water is involved, and longer-lasting efficacy can be expected.

[0087] (Bacterial MIC test · Mold MIC test) A chemical solution (Zn(TBZ)(BDC) (Example 1), Zn 4 (TBZ) 2 (BDC) 3 (Example 2) and TBZ, BDC, ZnCl 2 、Zn(NO 3 ) 2 ) were diluted to a predetermined concentration, and this diluted chemical solution was dispensed into 96-well plate wells, and bacterial MIC tests and mold MIC tests were performed under the following conditions. Bacterial MIC test: An inoculum of cultured bacteria (Escherichia coli, Staphylococcus aureus subsp. aureus) was dropped into the 96-well plate wells containing the chemical solution. Static culture was carried out at 31°C in the dark for 24 hours, 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 Table 3. Mold MIC test: An inoculum in which spores and hyphae (Aspergillus niger, Trichoderma virens) obtained by culturing were dispersed was dropped into the 96-well plate wells containing the chemical solution. Static culture was carried out at 26°C in the dark for 7 days, and the MIC (minimum inhibitory concentration) (mg / L), which is the lowest concentration at which no mold growth was observed, was determined. The results are shown in Table 3.

[0088]

Table 3

[0089] In the MIC tests, the samples obtained in Examples 1 and 2 both showed good antibacterial and antifungal activities. By using a coordination polymer composed of thiabendazole, terephthalic acid, and zinc, it is suggested that zinc and thiabendazole are each released in appropriate amounts as appropriate, and each component exhibits a good effect against the pests targeted.

[0090] (Weather resistance test after kneading polycarbonate resin) Each component of Zn(TBZ)(BDC) (Example 1) and TBZ was mixed with an aromatic polycarbonate resin (“Iupilon S-2000” manufactured by Mitsubishi Engineering-Plastics Corporation) so that the content of TBZ was 1%, and then supplied to a twin-screw kneading extruder (a co-rotating twin-screw kneading extruder HK-25D(41D) manufactured by Parker Corporation), kneaded under the conditions of a screw rotation speed of 150 rpm and a kneading temperature of 270 °C (actual measured resin temperature 290 °C), and pelletized using a pelletizer to obtain pellets of each aromatic polycarbonate resin composition of Zn(TBZ)(BDC) (Example 1) and TBZ. After drying the above pellets and the pellets without added drug (BL) at 100 °C, injection molding was performed using an injection molding machine (a small electric injection molding machine SE18DUZ manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 270 to 290 °C, a mold temperature of 80 °C, and a molding cycle of 40 seconds or 300 seconds to produce plate test pieces with a thickness of 40 × 40 × 2 mm. Using the obtained plate test pieces, weather resistance treatment (ultraviolet intensity: 180 W / m 2 , treatment time: 100 h) was carried out using a super xenon weather meter. The results are shown in Figure 6. Compared with the resin kneaded with TBZ, the resin kneaded with Zn(TBZ)(BDC) has less yellowing.

[0091] (Antibacterial test using plate test pieces) An antibacterial test was performed using the plate test pieces obtained in the above weather resistance test (without weather resistance treatment using a super xenon weather meter). In accordance with JIS-Z-2801, Escherichia coli and Staphylococcus aureus subsp. aureus were used as test bacteria. The test specimens were placed on plastic petri dishes, and the test bacteria pre-cultured on ordinary agar medium were each diluted with NB medium to obtain inoculation bacterial solutions. The solutions were dropped onto the samples, covered with films, and cultured in a thermo-hygrostat (35 ± 1 °C, relative humidity 95%). After 24 hours, the surfaces of the test specimens and the films were washed out using SCDLP medium. The number of bacteria per 1 ml of the washed-out liquid was calculated by the agar plate culture method using ordinary agar medium, and the number of bacteria per 1 cm of the sample was determined. 2 was determined. The antibacterial test results are shown in Table 4. Zn(TBZ)(BDC) had an antibacterial activity value of 2 or more against BL (blank), and an antibacterial effect was observed.

[0092]

Table 4

[0093] Even when incorporated into polycarbonate resin that requires molding at high temperatures, Zn(TBZ)(BDC) was shown to be effective because of its excellent heat resistance.

[0094] (Mold prevention test using plate test specimens) A mold prevention test was conducted using the plate test specimens obtained in the above weather resistance test (after weathering treatment using a super xenon weather meter). The mold prevention test was carried out in accordance with Test B Method for Plastic Products in Appendix A of JIS Z 2911:2018. Each test specimen was placed on a glucose-added inorganic salt agar medium, and a mixed spore suspension of Aspergillus niger, Penicillium pinophilum, Paecilomyces variotii, Trichoderma virens, and Chaetomium globosum was sprayed, and then cultured at 29 °C. After a certain period of time, the mold growth on the samples was evaluated in six grades (0: no mold growth visible to the naked eye and under the microscope ~ 5: mycelia covering the entire sample confirmed by the naked eye) based on the following criteria. Table 5 shows the results of the anti - mold test using plate test specimens after weathering treatment with a super xenon weather meter. At 4 weeks after the start of the test, compared with the polycarbonate resin kneaded with TBZ, the one kneaded with Zn(TBZ)(BDC) had the growth of mold suppressed.

[0095]

Table 5

[0096] Zn(TBZ)(BDC) was shown to be excellent in terms of weather resistance.

[0097] The coordination polymer containing thiabendazole, terephthalic acid and zinc has reduced color tone change due to light and heat, is difficult to decompose even when heated at high temperature, is difficult to elute in water, and is excellent in weather resistance. It can be widely used for pest control such as anti - mold applications and antibacterial applications.

[0098] (Anti - virus test with hard - coat film) A hard - coat film was prepared and its efficacy against bacteriophage Qβ was confirmed.

[0099] Coating film formation Using an automatic coating device (PI - 1210 manufactured by Tester Sangyo Co., Ltd.), approximately 3 mL of a coating material solution (ethanol 81.06, KBM - 503 (manufactured by Shin - Etsu Chemical Co., Ltd.) 8.74, organosilica sol IPA - ST (manufactured by Nissan Chemical Industries, Ltd.) 3.5, 2 - methyl - 4'-(methylthio)-2 - morpholinopropiophenone 0.2, Aluminum acetylacetonate 1.5, Zn(TBZ)(BDC) 5 (unit: Wt%)) was applied to a biaxially stretched polyester (PET) film (Lumirror (R) film T60 transparent 250μm 148×210mm) manufactured by Toray Industries, Inc. Then, it was dried in a constant - temperature bath at 100°C for 1 minute and solidified using an ultraviolet - curing light source device (manufactured by Eye Graphics Co., Ltd.).

[0100] Antiviral test The antiviral test of the hard coat film prepared in accordance with JIS R 1756:2020 "Fine Ceramics - Test Method for Antiviral Property of Visible Light Responsive Photocatalyst Materials - Method Using Bacteriophage Qβ" was conducted. However, the test piece (hard coat film) inoculated with the test solution was only left standing in the dark without light irradiation. After treating the hard coat film with bacteriophage and leaving it standing for 4 hours, the bacteriophage infectious titer was measured using Escherichia coli.

[0101] As a result, the hard coat film prepared by adding Zn(TBZ)(BDC) showed a higher antiviral activity value and excellent activity compared to the hard coat film prepared by adding TBZ instead of Zn(TBZ)(BDC).

Claims

1. A coordination polymer containing thiabendazole (TBZ), terephthalic acid (BDC), and zinc (Zn).

2. Formula (I) [Zn a (TBZ) b (BDC) c R d n (I)​ (In the formula, R represents the counter anion of zinc ions. a, b, and c represent integers of 1 or more, and d represents an integer of 0 or more. n is Zn a (TBZ) b (BDC) c R d is the number of sets of structural units represented by, and is not particularly limited) The coordination polymer according to Claim 1, which is a compound represented by the formula or a solvate thereof.

3. [Zn(TBZ)(BDC)]n or [Zn ４ (TBZ) 2 (BDC) 3 n (wherein n is the number of sets of constitutional units represented by Zn(TBZ)(BDC) or Zn ４ (TBZ) 2 (BDC) 3 and is not particularly limited), the coordination polymer according to claim 1 or 2.

4. A pest control composition comprising the coordination polymer according to any one of Claims 1 to 3.

5. The pest control composition according to Claim 4, further comprising any one of an antimicrobial component, an insecticide, a herbicide, and a plant growth regulator.

6. The pest control composition according to Claim 4 or 5, which is used as a microbial contamination control agent for industrial products.

7. The pest control composition according to Claim 6, wherein the pest control composition is a resin composition.

8. The pest control composition according to Claim 6, wherein the pest control composition is a fiber or a thread.

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