TW202228515A - Coordination polymer and composition containing same for pest control - Google Patents

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

Coordination polymer and pest control composition containing the same

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

Dipirin is widely used as a fungicide, antifungal agent, preservative, insect repellant, etc. For example, as described in Patent Documents 1 to 4, albiline is used for wood products, paper, PVC (polyvinyl chloride, polyvinyl chloride), and the like for the above-mentioned purpose. Albiline itself has a certain degree of stability, but it is decomposed or colored by light (ultraviolet rays), and decomposed by heat (disappears under high heat). Such decomposition or disappearance may be suppressed by various complexation, that is, the stability of physical properties may be improved. However, the complex itself may be colored, or the complex itself may be colored by light or heat even if the complex itself is white. As a result, when it is used in the form of a composition, there is a problem that the color and texture of the material to be mixed are lost. On the other hand, Non-Patent Documents 1 and 2 describe a coordination polymer compound containing tiabiline, a polyvalent carboxylic acid, and a heavy metal ion. However, although the crystal structure is described in these documents, it is not described that the polyvalent carboxylic acid is terephthalic acid; the above-mentioned coordination polymer compound reduces the color change caused by light or heat, and is not easily decomposed even if high heat is applied. In addition, it is not described that the above-mentioned complex polymer compound is excellent in weather resistance and can be suitably used for biocide applications. prior art literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2017-165692 Patent Document 2: Japanese Patent Publication No. 2016-532788 Patent Document 3: Japanese Patent Publication No. 2015-516382 Patent Document 4: Japanese Patent Publication No. 2015-516381 Non-patent literature

Non-Patent Document 1: Bulletin of the Korean Chemical Society, Volume33, Issue 9, Pages: 2917-2924 (2012) Non-Patent Document 2: Chinese Journal of Structual Chemistry, 29 (2), 240-244 (2010)

[Problems to be Solved by Invention]

The object of the present invention is to provide a pest control composition containing albiline, which reduces the color change caused by light or heat, does not easily decompose even when high heat is applied, and suppresses water leaching . [Technical means to solve problems]

The inventors of the present invention have conducted repeated studies in order to achieve the above-mentioned object, and as a result, they have found that by using a coordination polymer containing alabiline, terephthalic acid, and zinc, it is possible to provide a alabiline-containing polymer that is not easily decomposed even when high heat is applied. The pest control composition has completed the present invention.

That is, the present invention includes the following aspects. (1) A coordination polymer containing tiabiline (TBZ), terephthalic acid (BDC), and zinc (Zn). (2) The coordination polymer according to (1), which is a compound represented by the formula (I) or a solvent adduct thereof, [Zn _a (TBZ) _b (BDC) _c R _d ] _n ( I) (wherein, R represents the counter anion of zinc ion; a, b and c represent an integer of 1 or more, d represents an integer of 0 or more; n is the structure represented by Zn _a (TBZ) _b (BDC) _c R _d The number of sets of units is not particularly limited). (3) The coordination polymer according to (1) or (2), which is represented by [Zn(TBZ)(BDC)] _n or [Zn ₄ (TBZ) ₂ (BDC) ₃ ] _n ( In this equation, n is the aggregate number of structural units represented by Zn(TBZ)(BDC) or Zn ₄ (TBZ) ₂ (BDC) ₃ , which is not particularly limited). (4) A pest control composition comprising the coordination polymer according to any one of (1) to (3). (5) The pest control composition according to (4), which further comprises 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 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 as described in (6), wherein the pest control composition is fiber or yarn. [Effect of invention]

The coordination polymer containing tiabiline of the present invention is not easy to change color tone due to light or heat, is not easy to decompose even if high heat is applied, and is not easy to cause leaching of water, so it is particularly suitable for outdoor applications where light is irradiated. There may be areas where high heat is applied, and scenes where there are many opportunities to come into contact with water, etc.

The composition for pest control of the present invention contains a coordination polymer containing tiabiline, terephthalic acid, and zinc.

(1) Coordination macromolecule containing tibilin Coordination polymers containing tabiline, terephthalic acid, and zinc (hereinafter, referred to as "tabiline-containing coordination polymers") have different polymer structures depending on the type of zinc, but all are used as pest control Excellent composition. The coordination polymer is a complex having a continuous structure including a polydentate ligand and a metal ion. For example, a coordination macromolecule linked by a (-M-L-M-L-) structure can be generated from a two-dentate ligand L and a two-coordinated metal ion M. In coordination polymers, metal ions are located in the main chain. In the case of the present invention, depending on the type of zinc salt, coordination polymers with different dimensional structures can be obtained. The structure of the coordination polymers is not particularly limited, and no matter what kind of structure, it can be obtained due to light or heat. A composition for pest control containing albiline in which the change in color tone is reduced, the composition is not easily decomposed even when high heat is applied, and water leaching is suppressed.

The coordination polymer of the present invention is represented by the following formula (I), [Zn _a (TBZ) _b (BDC) _c R _d ] _n (I) Zn _a (TBZ) _b (BDC) _c R _d Each structural unit is connected by a coordinate bond. It can be a solvent adduct in which the solvent is incorporated into the coordination polymer. In formula (I), TBZ represents albiline, BDC represents terephthalic acid, and R represents the counter anion of zinc ion. The counter anion is the anion part of the zinc compound, and examples thereof include halogen anions of F, Cl, Br, or I; inorganic anions such as NO ₃ and SO ₄ ; and organic anions such as HCOO, CH ₃ COO, and acac. a, b and c each independently represent an integer of 1 or more, specifically, any integer in the range of 1 to 50, 1 to 10, 1 to 5, etc., and d represents an integer of 0 or more, specifically, represents Any integer in the range of 0-50, 0-10, 0-5, etc. n is the aggregate number of structural units represented by Zn _a (TBZ) _b (BDC) _c R _d , and is not particularly limited as long as the effects of the present invention can be exhibited.

Specifically, as shown in the Examples, the structural unit may be a coordination polymer such as Zn(TBZ)(BDC), Zn ₄ (TBZ) ₂ (BDC) ₃ ･6DMF, or the like. Here, DMF represents N,N-dimethylformamide as a solvent. For example, in the case of a coordination polymer in which the structural unit shown by the molecular model of FIG. 2 is Zn(TBZ)(BDC), in each structural unit, there are two N atoms in TBZ of one molecule. 1 Zn ion (Zn1: coordination number is 6) coordinated with 2 O atoms of one COOH group in BDC of 2 molecules, each structural unit is formed by making 2 O atoms of one COOH group in BDC The Zn ions (Zn1) of other structural units are coordinately bonded and connected in a straight chain. Furthermore, in the case where the structural unit shown by the molecular model of FIG. 3 is a coordination polymer of Zn ₄ (TBZ) ₂ (BDC) ₃ ･6DMF, four zinc ions in each structural unit have one molecule 2 zinc ions (Zn1: coordination number is 4) in which 1 N atom in TBZ is coordinated with 1 O atom in one COOH group in 3 molecules of BDC, and 2 zinc ions in 1 molecule of TBZ. The remaining 2 N atoms coordinate with 1 O atom of one COOH group in the BDC of 3 molecules of zinc ions (Zn2: coordination number is 5), each structural unit is formed by making the N atom in TBZ and The O atom in the BDC is coordinately bonded to the zinc ions (Zn1 and Zn2) of other structural units and connected in a network, as a result, one-dimensional channel pores are formed. In addition, 6 DMF as a solvent are incorporated into each structural unit.

(Albiline: TBZ) Albiline is a compound represented by the following formula, and is well known as a fungicide or the like. [hua 1]

(Terephthalic acid: BDC) The terephthalic acid is a compound represented by the following formula. [hua 2]

(zinc salt) Zinc salts are divalent inorganic or organic zinc salts. Examples of the inorganic salt include salts of inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and halides such as chloride, bromide, and iodide. Examples of the organic salt 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, nitrate, acetate, sulfate, chloride, bromide, iodide, and lactate are preferred. These zinc salts may be used alone or in combination of two or more.

(solvent) The solvent used in the synthesis is not particularly limited, and an organic solvent, water, or a mixed solvent of these can be used. The solvent may be used alone, or a mixed solvent of two or more may be used. The organic solvent is not particularly limited, and specific examples include alcohol compounds such as methanol, ethanol, and propanol; ether compounds such as diethyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; and aromatic compounds such as benzene and toluene. Hydrocarbons; halogenated hydrocarbons such as dichloromethane and chloroform; acetone, ethyl acetate, acetonitrile, N,N-dimethylformamide (DMF), N,N-diethylformamide, N,N-dimethylformamide Ethylacetamide, etc. Among these, N,N-dimethylformamide is preferably used. These solvents may remain in the coordination polymer within the range that does not interfere with the purpose of pest control.

(2) Preparation of coordination polymers containing tibilin In a solvent, tabiline, terephthalic acid, and a zinc salt are mixed, whereby a tabiline-containing coordination polymer can be obtained. The conditions at the time of mixing are as follows.

Regarding the mixing ratio of zinc salt and terephthalic acid, the molar ratio of zinc salt:terephthalic acid=1:5 to 5:1 is preferable, and the range of 1:1 to 4:1 is more preferable. Regarding the mixing ratio of the zinc salt and the albiline, the range of the molar ratio of the zinc salt:albiline=1:5 to 5:1 is preferable, and the range of 1:2 to 2:1 is more preferable.

When the reaction is carried out in a solvent, the molar concentration of the zinc salt in the solvent is preferably 0.005-5 mol/L, more preferably 0.01-2 mol/L. The molar concentration of terephthalic acid is preferably 0.001-5 mol/L, more preferably 0.005-2 mol/L. The molar concentration of tiabiline is preferably 0.001-5 mol/L, more preferably 0.005-2 mol/L.

The coordination polymer containing tiabiline can sometimes be obtained by simply mixing zinc salt, terephthalic acid and tibitrene, or it can also be added to a pressure-resistant container such as an autoclave, and the reaction is carried out under high temperature and pressure. . The heating temperature of the reaction solution is not particularly limited as long as a coordination polymer exhibiting the above-mentioned predetermined properties can be obtained, and it is preferably in the range of room temperature to 200°C. In the case of heating, it is preferably 100 to 150°C.

The reaction time of the present production method is not particularly limited, as long as a coordination polymer exhibiting the above-mentioned predetermined characteristics can be obtained, and it is preferably 1 hour or more, and more preferably 24 hours, in terms of a more excellent product yield. hours or more. In the case of room temperature, it is preferably 24 hours or more, and the heating time in the heating step is preferably 6 hours or more.

The procedure of the present production method is not particularly limited, as long as a coordination polymer exhibiting the above-mentioned predetermined characteristics can be obtained. For example, the following method can be preferably exemplified: in the presence of a solvent, Diformic acid and zinc salt are mixed and heated. In this production method, the mixing method of the reaction substrate is not particularly limited, and a known method can be used. In addition, the order of adding each component is not particularly limited, and the above-mentioned components may be added to the reaction vessel at the same time, or may be added sequentially.

After the reaction in the above reaction system, the product and the solvent can be easily separated by separation methods such as filtration or centrifugation. Furthermore, the products prepared in the above steps can be separated and purified by separation methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography or a combination of these separation methods. After filtration, it is preferably washed sufficiently with a solvent that dissolves terephthalic acid and zinc salt of the raw materials, and it is preferably vacuum-dried at 100°C to 150°C. As the present solvent, for example, the same solvent as the solvent used in the above synthesis can be used.

Confirmation of the structure, composition and properties of the product can be performed using general methods. For example, X-ray diffraction measurement (confirmation of crystal structure), 13C-CPMAS-NMR measurement (composition analysis of product), thermal analysis (measurement of heat resistance) and the like can be used. X-ray diffraction measurement or 13C-CPMAS-NMR measures the powder directly at room temperature, and thermal analysis measures by heating the powder from room temperature to 1000°C in air.

(3) Arbitrary ingredients The pest control composition of the present invention may contain only the above-mentioned components, or may contain the following components.

(A) Resin As the resin contained in the pest control composition of the present invention, various resins can be used depending on the application of the pest control composition, required performance, and the like. As the resin, a thermoplastic resin and a thermal or photocurable resin may, for example, be mentioned. These may be used individually by 1 type, and may use 2 or more types together.

a) Thermoplastic resin The thermoplastic resin used in the present invention is not particularly limited, and specifically, styrene-based resins, acrylic resins, vinyl acetate resins, acrylonitrile copolymers, polyphenylene ether resins (PPO), and polysiloxane resins can be exemplified. (PSF, PSU), Polyetherimide (PES), Polyarylate (PAR), Polyetherimide (PEI), Polyimide (PAI), Polyimide (PI), Polymethyl Methyl acrylate, 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 (PET), Polyvinyl Chloride (PVC), Polyethylene, Polyethylene Propylene, Synthetic Thermoplastic Polyolefin (TPO), Styrene-Butadiene-Styrene (SBS), Styrene-Butadiene Rubber (SBR), Hydrogenated SBS, Styrene-Isoprene-Styrene (SIS) , various olefin elastomers, various polyester 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), polyether resin (PES, PESU), Polyphenylene sulfide (PPSU), polyether ketone (PEK), polyether ether ketone resin (PEEK), polyether, polyacrylate, liquid crystal polyester resin, liquid crystal polymer (LCP), polyamide resin (nylon), Fluorine resin, polyvinylpyrrolidone (PVP), etc.

b) heat or light hardening resin The thermally or photocurable resin used in the present invention is not particularly limited, and monomers, prepolymers, oligomers having vinyl groups, (meth)acryloyl groups, epoxy groups, and oxetanyl groups can be used. materials, polymers, etc. Among them, it is preferable to use a polyfunctional resin. In addition, in this invention, "(meth)acryloyl group" means "acryloyl group" and/or "methacryloyl group".

Specifically, polyfunctional or monofunctional (meth)acrylate monomers, acrylate oligomers, and the like can be used for the above-mentioned thermally or photocurable resin. Among them, polyfunctional acrylates and the like containing two or more polymerizable unsaturated groups are preferred.

The above-mentioned monofunctional acrylate monomers are monomers having one (meth)acrylate group in the molecule, for example, tricyclodecane acrylate, isopropyl acrylate, tetrahydrofurfuryl acrylate, Phenoxyethyl acrylate, etc. In addition, in this invention, "(meth)acrylate group" means "acrylate group" and/or "methacrylate group".

In addition, the above-mentioned polyfunctional acrylate monomer is a monomer having 2 or more, preferably 2 to 6 (meth)acrylate groups in the molecule, for example, tricyclodecane dimethanol dimethanol Acrylates, Neopentyl Glycol Diacrylate, Hydroxypivalate Neopentyl Glycol Diacrylate, Diethylene Glycol Diacrylate, Trimethylolpropane Triacrylate, Pentaerythritol Triacrylate, Pentaerythritol Tetraacrylate , Di-trimethylolpropane tetraacrylate, bisphenol A polyethoxylate diacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, etc.

Moreover, as an acrylate oligomer, an epoxy acrylate oligomer, a polyester polyacrylate oligomer, a urethane acrylate oligomer, etc. are mentioned, for example.

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

Specifically, for example, silicone resin, polysiloxane resin, acrylic polysiloxane resin, epoxy resin, polyurethane, phenolic resin, melamine resin, urea resin, unsaturated polyester resin, Silicone resin and diallyl phthalate resin, etc.

(B) Solvent The pest control composition of the present invention may further contain a solvent capable of dispersing or dissolving a complex polymer containing tibilidine, terephthalic acid, and zinc, or a mixture of a complex polymer and a resin. The solvent is not particularly limited, and examples include water; organic acids such as formic acid, acetic acid, lactic acid, oxalic acid, citric acid, and benzoic acid; alcohols such as methanol, ethanol, isopropanol, isobutanol, and n-butanol; Ethanolamine, dimethylamine, pyridine and other amines; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and other amides; acetone, methyl ethyl ketone, methyl isobutyl Ketones such as ketones, cyclohexanone, and acetone acetone; ethers such as diethyl ether, dimethyl ether, tetrahydrofuran, etc.; alcohols containing ether groups such as ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ethyl acetate , butyl acetate, ethyl lactate, butyl lactate and other esters; hexane, benzene, xylene, toluene and other hydrocarbons; methylene chloride, carbon tetrachloride, chloroform, trichloroethylene and other halogenated hydrocarbons; acetonitrile; Mineral oil, synthetic hydrocarbon oil, synthetic ester oil, natural oil, natural oil derivatives, ether oil, silicone oil, fluorine oil, etc. These solvents may be used alone or in combination of two or more.

(C) Other In the pest control composition of the present invention, various components may be further added according to the purpose within a range not impairing the effects of the present invention. Examples of such components include flame retardants, heat stabilizers, antioxidants, lubricants, antistatic agents, ultraviolet inhibitors, colorants, release agents, heat insulating agents, dispersants, surfactants, pH Conditioners, antifoaming agents, rust inhibitors, viscosity modifiers, metal chelating agents, friction modifiers, other antibacterial ingredients, bactericidal ingredients, antiviral ingredients, antifungal ingredients, antiseptic ingredients and other ingredients with antimicrobial properties, insecticides pesticides, herbicides, plant growth regulators. These can be used in combination of two or more.

(Flame Retardant) The flame retardant is not particularly limited, and for example, halogen-based flame retardants such as chlorine-based and bromine-based flame retardants; organic-based flame retardants such as phosphorus-based flame retardants; nitrogen-containing flame retardants, antimony-based flame retardants, metal hydrogen flame retardants, etc. Inorganic flame retardants such as oxide-based flame retardants, boron-based flame retardants (boric acid flame retardants), and red phosphorus-based flame retardants. These can be used in combination of two or more.

(Heat stabilizers) Although it does not specifically limit as a heat stabilizer, For example, phosphorus-based heat stabilizers, such as a phosphite and a phosphoric acid ester, are mentioned. Examples of the phosphite include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and trinonyl phosphite. ester, tridecyl phosphite, trioctyl phosphite, tri-octadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, Monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis(2,6-di-tert-butylene) Tri-esters of phosphites such as 4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis[(4,6-di-tert-butylphenyl)octyl phosphite], Diesters, monoesters, etc. Examples of phosphoric acid esters include: trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl) phosphate, 2-phosphoric acid -Ethylphenyl diphenyl ester, tetrakis(2,4-di-tert-butylphenyl)-4,4-diphenylphosphinate, etc.

(Antioxidants) Although it does not specifically limit as an antioxidant, For example, a phenol type antioxidant, a phosphorus type antioxidant, a phosphite type antioxidant, a thiourea type antioxidant, etc. are mentioned.

(lubricant) Although it does not specifically limit as a lubricant, For example, higher fatty acid, ester waxes, polyethylene waxes, metal soaps, etc. are mentioned.

(Antistatic agent) It does not specifically limit as an antistatic agent, For example, a fatty acid amine, a fatty acid alcohol, a fatty acid ester, a fatty acid amide, a sulfonic acid compound, etc. are mentioned.

(UV inhibitor) Although it does not specifically limit as an ultraviolet-ray inhibitor, For example, a salicylic acid derivative compound, a benzophenone compound, a benzotriazole type compound, such as a benzotriazole derivative, a cyanoacrylate compound, etc. are mentioned.

(Colorant) It does not specifically limit as a coloring agent, For example, an organic pigment, an inorganic pigment, a dye, a brightener, etc. are mentioned. Examples of organic pigments include phthalocyanine-based, benzimidazolone-based, azo-based, azomethine-based, azomethine-based, anthraquinone-based, pyrenone/perylene-based, indigo/thioindigo-based, As inorganic pigments, for example, extender pigments, titanium oxide-based pigments, iron oxide-based pigments, etc. Pigments, spinel pigments, etc. More specifically, insoluble azo pigments such as toluidine red, toluidine violet red, Hansa yellow, benzidine yellow, and pyrazolone red can be used; rissol red, Helio Bordeaux, scarlet pigment, permanent red 2B, etc. Soluble azo pigments; phthalocyanine series such as phthalocyanine blue and phthalocyanine green; quinacridone series such as quinacridone red and quinacridone magenta; perylene series such as perylene red and perylene scarlet; isoindolinone yellow , isoindolinone series such as isoindolinone orange; pianthrone series such as picanthrone red, picanthrone orange; thioindigo series, condensed azo series, benzimidazolone series, quinophthalone yellow, Nickel azo yellow, pyrene orange, anthrone orange, dianthraquinone red, bismuth violet and other previously known pigments. As the dye, for example, conventionally known dyes such as direct dyes, basic dyes, cationic dyes, acid dyes, mordant dyes, acid mordant dyes, sulfur dyes, naphthol dyes, disperse dyes, and reactive dyes can be mentioned. As a brightener, aluminum paste, mica, scaly iron oxide, etc. are mentioned.

(Release agent) The release agent is not particularly limited, and examples include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbons with a number average molecular weight of 200 to 15,000, polysiloxane-based polysiloxane oils, etc. . As aliphatic carboxylic acid, saturated or unsaturated aliphatic monobasic, dibasic or tribasic carboxylic acid can be mentioned. Here, the term "alicyclic carboxylic acid" also includes alicyclic carboxylic acid. Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, tartaric acid, ceric acid, besearic acid, and stearic acid , montanic acid, adipic acid, azelaic acid, etc. As the aliphatic carboxylic acid in the ester of aliphatic carboxylic acid and alcohol, the same as the aliphatic carboxylic acid described above can be used. As an alcohol which reacts with this aliphatic carboxylic acid and forms an ester, a saturated or unsaturated monohydric alcohol, a saturated or unsaturated polyhydric alcohol, etc. are mentioned. Here, aliphatic also includes alicyclic compounds. Specific examples of these alcohols include octanol, decyl alcohol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyl Perfluoropropanol, neopentyl glycol, di-trimethylolpropane, dipentaerythritol, etc. These ester compounds of aliphatic carboxylic acid and alcohol may contain aliphatic carboxylic acid and/or alcohol as impurities, or may be a mixture of a plurality of compounds.

Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myristyl palmitate as a main component), stearyl stearate, behenate behenate, hard behenate Fatty esters, glycerol monopalmitate, glycerol monostearate, glycerol distearate, glyceryl tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, Pentaerythritol Tristearate, Pentaerythritol Tetrastearate. Examples of the aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Here, aliphatic hydrocarbons also include alicyclic hydrocarbons. Also, these hydrocarbon compounds may be partially oxidized. Examples of the polysiloxane-based polysiloxane oil include dimethyl polysiloxane oil, phenylmethyl polysiloxane oil, diphenyl polysiloxane oil, and fluorinated alkyl polysiloxane oil. These may be used alone or in combination of two or more.

(insulation agent) The heat insulating agent is not particularly limited, as long as it is a general user of those skilled in the art, such as infrared (near infrared) shielding agents, absorbing pigments, and reflective pigments (heat shielding pigments).

(Dispersant) Dispersants are additives used to uniformly disperse solid particles such as inorganic and organic pigments in a medium to prepare stable dispersions. It will not specifically limit as long as the objective of particle dispersion can be achieved, For example, various surfactants etc. can be used.

(surfactant) As a surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, etc. are mentioned. Examples of nonionic surfactants include polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene aryl phenyl ethers, polyoxyalkylene alkyl ethers, sorbitan fatty acid esters, polyoxyalkylene Oxyalkylene sorbitan fatty acid ester, polyoxyalkylene vegetable oil, etc. Examples of anionic surfactants include alkylbenzenesulfonates, alkylnaphthalenesulfonates, ligninsulfonates, naphthalenesulfonate formaldehyde condensates, polyoxyethylene alkyl ether sulfates, polyoxyethylene Oxyethylene alkyl phenyl ether sulfate, dialkyl sulfosuccinate, etc. As a cationic surfactant, an aliphatic amine salt, a quaternary ammonium salt, etc. are mentioned, for example. Examples of the amphoteric surfactant include alkylbetaine-type surfactants, amidopropylbetaine-type surfactants, imidazolinium betaine-type surfactants, and sulfobetaine-type surfactants. , Phosphobetaine-type surfactants, etc. These surfactants may be used alone or in combination of two or more.

(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, or salts thereof; inorganic acids such as phosphoric acid, polyphosphoric acid, and boric acid, or salts thereof.

(Defoamer) Although it does not specifically limit as an antifoamer, For example, an antifoamer, such as a mineral oil type, a polysiloxane type, a polyether type, a fluoroalkyl ether, and a polyalkylene glycol type, is mentioned.

(Rust inhibitor) It does not specifically limit as a rust inhibitor, For example, metal sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, organic phosphite, organic phosphate, organic sulfonic acid metal salt, Organophosphate metal salts, alkenyl succinates, polyol esters, benzotriazole-based compounds, and the like.

(viscosity modifier) Although it does not specifically limit as a viscosity modifier, For example, Sanxian gum, carboxymethyl cellulose, hydroxyethyl cellulose, acacia, gellan gum, polytridextrose, etc. are mentioned.

(metal chelating agent) The metal chelating agent is not particularly limited, and examples thereof include ethylenediaminetetraacetic acid or its salt, nitrotriacetic acid or its salt, diethylenetriaminepentaacetic acid or its salt, hydroxyethylethylenediamine Triacetic acid or its salt, triethylenetetraminehexaacetic acid or its salt, 1,3-propanediaminetetraacetic acid or its salt, 1,3-diamino-2-hydroxypropanetetraacetic acid or its salt, 1-hydroxyl Ethylene-1,1-diphosphonic acid or its salt, hydroxyethyliminodiacetic acid or its salt, dihydroxyethylglycine or its salt, glycol ether diaminetetraacetic acid or its salt, dihydroxyethylglycine or its salt Carboxymethylglutamic acid or its salt, nitrogen trimethylene phosphoric acid or its salt, etc.

(friction modifier) It does not specifically limit as a friction modifier, For example, a fatty acid, a fatty acid ester, an alcohol, etc. are mentioned.

(Other antibacterial ingredients, bactericidal ingredients, antiviral ingredients, antifungal ingredients, antiseptic ingredients and other ingredients with antimicrobial properties) Components having antimicrobial properties, such as other antibacterial components, bactericidal components, antiviral components, antifungal components, and preservative components, can be used without particular limitation. The active ingredient used may be liquid or solid, organic compound or inorganic compound, and may be a single compound or a mixture. These can be mixed and used in arbitrary ratios, and it can also be used by using 1 type of component or in combination of a plurality of components.

Hereinafter, specific examples are shown. Examples of antibacterial, bactericidal, antiviral, antifungal, and antiseptic ingredients include: benzimidazole-based compounds such as paroxetine, befenti, albiline, and dopamine; Phenyl carbamate series compounds; Dicarboxyimide series compounds such as Promethazine, Iptonin, Minkenin; Saifuzao, Fickli, Ducli, Iprozole, Dekeli, Dakeli, Huanke azoles, such as block, pulclide, hosid, triadimefon, metezole, micone, etanerate, saiforin; acylalanine compounds such as methallot; Formamide-based compounds such as fodolin and sulfamethoxazole; organic phosphorus-based compounds such as dexamethasone, aluminum triethylphosphonate, and white powder pine; anilinopyrimidine-based compounds such as pyrimethamine, minpirin, and cypro; Cyanopyrrole compounds such as Hutaning and Seed dressing; antibiotics such as blasticidin S, Gashimycin, polyoxomycin, velimycin; Shouxin, SSF-126 and other methoxy acrylate compounds; Acetate Kerejing, Kerejing alkane benzene sulfonate, Penfufen, Tetrachloroisobenzene, Dysenzinc-manganese, Gapudan, Forpe , Oxycin copper, alkaline copper chloride, trisazole, pyridoxine, culling fever, tetrachlorophthalide, Kejue, damifen, CGA245704, vasoxalin, oxolinic acid, fugiamine, rich Mi Zong, Ke Chlor Zong, Chlorbenzimidone, Thiophthalimidoxybisphenoxyarsine, 3-iodo-2-propylbutylcarbamate, Dithiophthalimidoxybisphenoxyarsine Decyldimethylammonium 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 and other quaternary ammonium salt compounds , Polyhexamethylene biguanide (PHMB), polyhexamethylene guanidine (PHMG), biguanide compounds such as lohexidine gluconate, pyridinium compounds such as cetylpyridinium chloride and dodecylpyridinium chloride , 3-iodo-2-propynyl-butylcarbamate (IPBC) and other organic iodine compounds, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine (TCMSP) ) and other pyridine-based compounds, pyridinethione-based compounds such as zinc pyrithione and sodium pyridinethione, benzothiazole-based compounds such as 2-(4-thiocyanatomethylthio)benzothiazole, 2-benzimidazolamine Methyl formate, imidazole-based compounds such as 2-(4-thiazolyl)-benzimidazole, thiocarbamate-based compounds such as tetramethylthiuram disulfide, 2,4,5,6-tetrakis Nitrile compounds such as chloroisophthalonitrile, N-(fluorodichloromethylthio)-phthalimide, N-(fluorodichloromethylthio)-N,N'-dimethyl- Halogenated alkyl sulfides such as N-phenyl-thioamide, α-tert-butyl-α(p-chlorophenylethyl)-1H-1,2,4-triazole-1-ethanol (commonly known as Keli) and other triazole compounds, 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-octane yl-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-tert-octyl-4- Isothiazolin-3-one, 2-n-butyl-1,2-benzisothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one isothiazoline-based compounds, 2-bromo-2-nitro-1,3-propanediol, 2,2-dibromo-2-nitroethanol, 2,2-dibromo-3-nitropropionamide, etc. Bromine compounds, p-chloro-m-cresol, 4-chloro-3,5-xylenol, tris-1,3,5(2H,4H,6H)-triethanol, streptomycin, Dayoulong (DCMU) ), tiazolone, pyranone, benzuron, nicosulfuron, liulong, bisbutatrol, querazine, simazine, oxazolid, permethrin, cyanide, paitrazine , Promethazine, Bidarin, Benifene, Amethoxazole, Metazapyr, Ethoxyfenol, Bifenol, Brombutazone, Bromoxynil, Herbicide, Pyridoxine amine, fenfen grass, chlormethoxam, diclofenac, dithiochlor, clomazone, cyclamate, barnyard dicamba, pyrimifen, chlorfenapyr, oralin, propargyl 㗁Oxalon, flufenox, pyrimidine, cyclopentazone, silver zeolite, silver silica gel, silver zirconium phosphate, silver histidine complex, paraben, sodium benzoate, desulfuric acid Sodium Hydroacetate, Potassium Sorbate, Methylparaben, Methylene Dithiocyanate, Copper Chloride, Copper Hydroxide, Dyestuff, Lithium Salt, Sodium Salt, Potassium Salt, Magnesium Salt, Calcium Salt Wait.

(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, and the like. These components can be used without particular limitation. The active ingredient used may be liquid or solid, organic compound or inorganic compound, and may be a single compound or a mixture. These can be mixed and used in arbitrary ratios, and one kind of component or a plurality of components can also be used in combination. Hereinafter, specific examples are shown. As insecticides, there can be exemplified: Saifuning, Saimining, Diminin, Fenpronin, Fenhuali, Yihuali, Taiminin, Ananin, Bifenin, Leninin, Zhiminin, Seven Pyrethroid compounds such as Fluthrin, Efenin, Cyphenin, Permethrin, Puja Lenin, Pyrethrin, Siprofen; Lice, XMC (Xylene Monochloride, monochloroxylene), Jiabaoli, Bijiapu, Jiabaofu, Nanad, Fenoke, Mianlingwei, pyrene and other carbamate compounds; European Ferapone, Sedasone, Multimethasone, Triclosone, Asolin, Lebensong, Methyl toxophore, Yubizon, Taosi Song, Chlorpyrifos Methyl, Pyridazine, Baiyusong, Metadasone, Organophosphorus compounds such as damasone, terbutazone, Anguo, glutathione ethyl, glutathione methyl, vegetable and fruit phosphorus, and premethazone; Fenlon, Fluoxuron, Sulfamethoxazole, Tafenox, Hexadol, Novalone, Defulon, Trifulon, 4-Chloro-2-(2-Chloro-2-methylpropyl) -5-(6-Iodo-3-pyridinylmethoxy)pyridin-3(2H)-one, 1-(2,6-difluorobenzyl)-3-[2-fluoro-4- (trifluoromethyl)phenyl]urea, 1-(2,6-difluorobenzyl)-3-[2-fluoro-4-(1,1,2,3,3,3-hexafluoro Propoxy)phenyl]urea, 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiazide oxadiazol-4-one, 1-(2,6-difluorobenzyl)-3-[2-fluoro-4-(1,1,2,2-tetrafluoroethoxy)phenyl]urea Isourea-based compounds; new nicotine-based compounds such as Imidamide, imiprodil, nitenpyram, thiamethoxam, cyprodinil, konidin, saigopei, and datnam; Dan, bufungin, thiocyanate, fensuda, phenokine, fentox, fenpromite, bidaben, bailipfen, amison, thiodigram, butyl methicillin, kefanpai , Fenpromite, Paclitaxel, Bitiphen, Delfinol, Delfenre, Diphenox, Zolafenur, Index, Sulfluramid, Mimetidine, Abatine, Keambo, Pai Rela, bromfenprod, 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, dichloro Thiopyrimidine, boric acid, disodium octaborate tetrahydrate, borax, borax pentahydrate, p-dichlorobenzene, capric acid, etc.

As herbicides, there can be exemplified: Tris-based compounds such as fenoxine and methexidine; urea-based compounds such as futuron and isoproturon; hydroxybenzonitrile-based compounds such as bromoxynil and iodobenzonitrile; 2,6-Dinitroaniline-based compounds such as trifulin; Allyloxyalkanoic acid-based compounds such as 2,4-D, ticloxam, fluroxypyr, and chloropropionic acid; Benzouron, metsulfuron-methyl , nicosulfuron, methylflusulfuron, cyclosulfuron and other sulfonylurea compounds; imidazolinone compounds such as imazapyr, imazaquin, imazethapyr; Bispyribac Na salt, Bisthiobac Na salt , Asifphen Na salt, Sulfentrazone, Balacaril, Sulfentrazone, Flumesulfuron, Chlorfenapyr, Cyhalofop-Prop, Diflufenacil, Diflufen, Isoflufen Oxaflutole, Glufosam-ammonium, Glyphosate, Bendarone, Salbutan, Difencao, Herbicide, Flufenafen, etc.

As a plant growth regulator, maleic hydrazine, kemetol, ethephon, gibberellin, mepikat chloride, thidiazuron, trinexapyr, paclobutrazol, niconazole, etc. are mentioned. As an insecticide, 1S,3R,4R,6R- carbene-3,4-diol, 2,5- pyridine dicarboxylic acid dipropyl ester, etc. are mentioned.

(polymerization initiator) In the case of using a thermally or photocurable resin as the resin, a polymerization initiator may also be included. As the polymerization initiator, a photopolymerization initiator and a thermal polymerization initiator may, for example, be mentioned.

As a photopolymerization initiator that can be used in the present invention, for example, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [Darocure 2959: manufactured by Merck Corporation], α- Hydroxy-α,α'-dimethylacetophenone [Darocure 1173: manufactured by Merck], methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651 ] and other acetophenone-based initiators; benzoin ether-based initiators such as benzoin ether and benzoin isopropyl ether; and halogenated ketones, acylphosphine oxides, acyl phosphates, etc.

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

As the azo-based initiator, for example, 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] Amine], 2,2'-azobis[2-(hydroxymethyl)propionitrile], 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azo Bis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(dimethylisobutyrate), 2,2'-azobis[2-(2- imidazolin-2-yl)propane], 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide}, etc. Among these, azobis(isobutyronitrile) is preferable in terms of cost or versatility.

The peroxide-based initiator is preferably one that is easily decomposed at a temperature of 80°C or lower with a half-life of 10 hours, for example, benzyl peroxide, isobutyl peroxide, and cumene peroxyoctanoate. esters, etc. The peroxide-based initiator can be suitably selected with a short thermal polymerization time and relatively stable as a reactive composition before polymerization.

Such a polymerization initiator is blended in a range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the total of the curable resin. It is preferable to mix|blend in the range of 0.01-1 weight part with respect to 100 weight part of total curable resins.

(4) Manufacturing method of composition for pest control The composition for controlling pests of the present invention can be used as a complex macromolecule containing tiabiline. If necessary, after preparing a coordination polymer containing tibilin, it is mixed with other components such as resin. Regarding the mixing method, mixing can be performed by a previously known method, for example, when a resin is used, it can be produced by performing melt-kneading. Specifically, a method of mixing a predetermined amount of a thermoplastic resin, a coordination polymer containing albiline, and other additives prepared as necessary, and mixing using various mixers such as a roller and a Henschel mixer can be exemplified. Then, melt-kneading is performed using a Banbury mixer, a roll, a Brinell mixer, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, or the like.

The pest control composition containing the resin of the present invention is mainly used as a resin material for the manufacture (molding) of various products (molded products). The molding method thereof can be a previously known method without limitation, that is, a molded product is formed from a thermoplastic resin material. Concretely, the general injection molding method, the ultra-high-speed injection molding method, the injection compression molding method, the two-color molding method, the hollow molding method such as gas assist, the molding method using a heat insulating mold, and the molding method using a rapid heating mold can be exemplified. , foam forming (also including supercritical fluid), insert forming, in-mold coating (IMC) forming method, extrusion forming method, sheet forming method, thermoforming method, rotational forming method, lamination forming method, pressure forming method Wait.

There is no particular limitation on the compounding amount of the complex macromolecule containing tiabiline in the pest control composition of the present invention. It can be appropriately changed according to the person to be mixed.

In the case of using a resin, the compounding amount of the resin is not particularly limited, but it is preferably 1 to 1000 parts by weight relative to 1 part by weight of the complex macromolecule containing tiabiline. It is preferably 1 to 300 parts by weight.

When a solvent is used, the mixing amount of the solvent is not particularly limited, but it is preferably 1 to 1000 parts by weight with respect to 1 part by weight of the coordination polymer containing tiabiline. It is preferably 2 to 100 parts by weight.

The composition for controlling pests containing a resin of the present invention and a molded product thereof exhibit antimicrobial activities such as antibacterial activity, antifungal activity, and antiviral activity. Therefore, it can be suitably used for applications requiring antimicrobial properties, such as: spray containers, kitchen utensils and other water-wading products; food packaging materials, coverings, household waste coverings and other household products; rubber footwear and other sanitation products; Bathroom interiors, carpets, wall sheets, wallpapers, outdoor Japanese paper, floor materials, sealants, adhesives, coatings and other building materials; resin-based siding, ceramic-based siding, tiles and other building exterior materials; Diapers, napkins, incontinence pads and other absorbent fiber products, medical gowns, surgical gowns and other medical and sanitary products; disposable toilets, toilet lids and other sanitary products; pet changing pads, pet diapers, pet towels and other pet supplies; air purification Filters, air conditioners, humidifiers, dehumidifiers and other household appliances materials; packaging containers, food and beverage packaging; pharmaceutical packaging materials, eye drops containers, contact lenses, lenses, intraocular lenses, oral treatment appliances and other dental/medical materials , bedding, socks, underwear and other fiber products; shell components such as personal computer exterior materials, tablet terminal exterior materials; cosmetic materials such as foundation containers; toys for children; stationery; toys; surface of mobile phones/smart phones Membrane materials; water filtration materials; keyboards, mice, armrests, pressing buttons, etc., materials that people will touch, etc.

In addition, the pest control composition of the present invention can also be prepared with at least one selected from the group consisting of paints, pigments, inks, fibers, pulp, rubber, latex, adhesives, films, formulations, ceramic materials, and metalworking oils composition is preferably used. As for fibers, for example, natural fibers (plant fibers such as cotton and hemp; animal fibers such as silk, wool, rabbit hair, alpaca hair, and feathers; mineral fibers such as asbestos) can be suitably used, for example. Chemical fibers {synthetic fibers (polyamide fibers such as nylon and aromatic polyamide fibers; polyvinyl alcohol fibers such as vinylon; polyvinylidene chloride fibers such as vinylidene fibers; polyvinyl chloride fibers such as polyvinyl chloride fibers) polyester fibers; polyester fibers such as polyester fibers; polyacrylonitrile fibers such as polyacrylonitrile fibers and modacrylic fibers; polyolefin fibers such as polyethylene fibers, polypropylene fibers, and polystyrene fibers; polyamines Polyurethane fibers such as carbamate fibers; polyvinyl chloride fibers such as polyvinyl alcohol fibers; polyvinyl fluoride fibers such as fluorine fibers; phenolic fibers such as phenolic fibers; polyethers such as Rexe and Success Ester-based fibers; polylactic acid-based fibers such as polylactic acid fibers; polyalkylene paraben-based fibers such as benzoate fibers; polytetrafluoroethylene-based fibers; polyvinylidene-based fibers; polyurea-based fibers) , Regenerated fibers (cellulosic fibers such as rayon, mucilage rayon, high wet modulus viscose fiber, cupro fiber, tencel, lyocell, etc.; cupro rayon and other cupro-based fibers; casein fibers, vegetable fibers Protein fibers, regenerated silk fibroin and other protein fibers; trehalose fibers; chitin fibers; mannan fibers; rubber fibers), Semi-synthetic fibers (cellulose-based fibers such as acetate fibers, triacetate fibers, and oxidized acetate fibers; protein-based fibers such as Promix; chlorinated rubber; hydrochloric acid rubber), Inorganic fibers (glass fibers such as glass fibers; carbon fibers such as carbon fibers; metal fibers; ceramic fibers such as quartz fibers and alumina fibers)} and the like.

In the present invention, the form of the target fiber product may, for example, be yarn, rope, wire rope, cloth (woven fabric, knitted fabric, or nonwoven fabric). As a specific example, it can be widely used for: linens such as sheets, pillowcases, towels; various clothes such as pajamas, white coats, aprons, hats, school uniforms, uniforms; clothing and miscellaneous goods such as bags and shoes; car seats, chairs, strollers, etc. Seats and seat covers; curtains, wallpapers and other interior materials; air conditioner filters, vacuum cleaner filters and other filters; tents, sleeping bags and other outdoor products; masks and other sanitary products; refrigerator interior sheets, freezer covers, etc. Household or industrial materials.

The pest control composition of the present invention exhibits antimicrobial activities such as antibacterial activity, antifungal activity, and antiviral activity. Therefore, the present invention can be suitably used for various materials requiring antimicrobial properties.

Hereinafter, although an Example is shown, the technical scope of this invention is not limited to these. Example

Example 1: Coordination polymer of [Zn(TBZ)(BDC)] _n (hereinafter abbreviated as "Zn(TBZ)(BDC)") A suspension of formic 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 for reaction. After the reaction, the single crystal was obtained by slowly cooling from 130° C. to room temperature over 50 hours. For the obtained single crystal, the powder X-ray diffraction pattern was measured with CuKα line using a measuring apparatus Bruker D2PHASER. As a result, the powder X-ray measurement at 5° to 50° showed a diffraction pattern as shown in FIG. 1 . (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, 20.57, 23.472 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

As a result of X-ray structural analysis of the single crystal obtained in Example 1, it was confirmed to be a coordination polymer having a one-dimensional chain structure represented by Zn(TBZ)(BDC). The spatial information of the X-ray structural analysis is shown in Table 1, and the molecular model is shown in FIG. 2 .

[Table 1] Spatial Information of X-ray Structural Analysis of Zn(TBZ)(BDC) Zn(TBZ)(BDC) experimental C ₁₈ H ₁₀ N ₃ O ₄ SZn molecular weight 429.75 color colorless Crystal system unit cell size Monoclinic (a=Å), (b=Å), (c=Å) a=7.2558(2) b=20.6091(6) b=11.1997(4) α (degree) 90 β (degree) 96.739(10) γ (degree) 90 Volume of unit cell (Å ³ ) 1663.1 space group P 2 ₁ /C Z value 4

(Other measurement results) The measurement result of the crystal obtained in Example 1 by infrared spectrophotometer (FT-IR) is shown in FIG. 7 . In addition, the measurement result of 13C-CPMAS-NMR of the crystal obtained in Example 1 is shown in FIG. 8 .

Example 2: A complex polymer of [Zn ₄ (TBZ) ₂ (BDC) ₃ ･6DMF] _n (hereinafter, abbreviated as "Zn ₄ (TBZ) ₂ (BDC) ₃ ･6DMF") The reaction was carried out under the same conditions, except that zinc chloride was changed to zinc nitrate hexahydrate (0.595 g, 2 mmol).

The single crystal obtained in Example 2 was subjected to X-ray structural analysis, and as a result, it was confirmed that the structural units represented by Zn ₄ (TBZ) ₂ (BDC) ₃ ･6DMF were connected in a network and had coordination with one-dimensional channel pores. macromolecule. Zn ₄ (TBZ) ₂ (BDC) ₃ ･6DMF means that 6 molecules of DMF per unit are incorporated in the pores of Zn ₄ (TBZ) ₂ (BDC) ₃ . The spatial information of the X-ray structural analysis is shown in Table 2, and the molecular model is shown in FIG. 3 .

[Table 2] Spatial Information of X-ray Structure Analysis of Zn ₄ (TBZ) ₂ (BDC) ₃ ･6DMF Zn ₄ (TBZ) ₂ (BDC) ₃ ･6DMF experimental C ₅₃ H ₄₅ N ₉ O ₁₅ S ₂ Zn ₄ molecular weight 1373.63 color light yellow Crystal system unit cell size Triclinic (a=Å), (b=Å), (c=Å) a=9.2124(14) b=10.3317(16) b=18.583(3) α (degree) 87.188(5) β (degree) 79.167(5) γ (degree) 89.571(5) Volume of unit cell (Å ³ ) 1735.11 space group P-1 Z value 4

0 After that, the sample Zn ₄ (TBZ) ₂ (BDC) ₃ ･6DMF was allowed to stand in an environment of 150° C., and was dried under reduced pressure with a vacuum pump to remove the solvent (DMF). For the single crystal before and after solvent removal, the powder X-ray diffraction pattern was measured with CuKα line using a measuring apparatus Bruker D2PHASER. In the powder X-ray measurement at 5° to 50°, the diffraction pattern shown in Fig. 4 is displayed. A slight difference was observed in the powder X-ray diffraction pattern by removing the solvent. It is presumed that the interplanar spacing changes due to the strain relief of the lattice before and after removal of the solvent, but the influence on the skeleton is 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, 40.49, 44.08, 45.02 Zn ₄ (BDC _{) 3 (} ± 0.2 ± 0.2 ± 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

(thermal analysis) The samples and TBZ (comparative example) obtained in Examples 1 and 2 were pulverized in an agate bowl, and then measured by TG-DSC (thermal analyzer) "Mettler-Toledo TGA-DSC3+". The results are shown in FIG. 5 . Regarding the weight loss with the increase in the heating temperature, both Examples 1 and 2 were significantly slower than the Comparative Examples.

(Solubility test) 10 mg of the sample obtained in Example 1 was added to 50 mL of distilled water to make it into a saturated state, and after stirring at room temperature for a certain period of time with a stirring bar, it was filtered with a filter ( 0.2 μm), HPLC (high performance liquid chromatography, high performance liquid chromatography) analysis was performed to calculate the water solubility. As a result, the water solubility was 13.4 ppm for Zn(TBZ)(BDC) and 1.3 ppm for Zn ₄ (TBZ) ₂ (BDC) ₃ , which were significantly lower than 20.4 ppm for TBZ. Since the solubility to water is reduced, in the use scene of intervening water, the elution amount of the active ingredient in particular is suppressed, and the efficacy can be expected to be maintained for a longer period of time.

(Bacteria MIC test, mold MIC test) The 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 prescribed concentration, and the diluted medicinal solution was dispensed into the wells of a 96-well plate, and the bacterial MIC test and mold were carried out under the following conditions MIC test. Bacterial MIC test: The inoculum of the cultured bacteria (Escherichia coli, Staphylococcus aureus) was added dropwise to the wells of the 96-well plate in which the medicinal solution was dispensed. The cells were cultured at 31°C in the dark for 24 hours, and MIC (minimum inhibitory concentration) (mg/L) was determined at the lowest concentration at which no bacterial growth was observed. The results are shown in Table 3. Mold MIC test: The inoculum in which the spores and hyphae (Niger koji fungus, Trichoderma viridans) obtained by culture were dispersed was added dropwise to the wells of the 96-well plate in which the medicinal solution was dispensed. The cells were cultured in a dark place at 26°C for 7 days, and the lowest concentration at which no mold growth was observed, that is, MIC (minimum inhibitory concentration) (mg/L) was determined. The results are shown in Table 3.

[table 3] MIC(ppm) Element Escherichia coli Staphylococcus aureus black yeast Trichoderma viridans Zn(TBZ)(BDC) ^{25a 6.3a 11.7b 3.0b} Zn ₄ (TBZ) ₂ (BDC) ₃ 11 ^{a 2.8a 4.4b 2.2b} TBZ >1847 >1847 ^{6.3b 1.6b} BDC 762.3 95.3 >400 >400 ZnCl ₂ ^{13a 3.1a} >400 >400 Zn(NO ₃ ) ₂ ^{13a 3.1a} >400 >400 a: Concentration in terms of Zn in the total b: Concentration in TBZ in total

In the MIC test, the samples obtained in Examples 1 and 2 showed good antibacterial activity and antifungal activity. By preparing a coordination polymer including tiabiline, terephthalic acid and zinc, each of zinc and tihepin is appropriately released in an appropriate amount, thereby suggesting that each component exerts a good effect on the target pest.

(Weather resistance test after kneading polycarbonate resin) Zn(TBZ)(BDC) (Example 1) and each component of TBZ were mixed with aromatic polycarbonate resin ("Iupilon S -2000", manufactured by Mitsubishi Engineering-Plastics Co., Ltd.), and then supplied to a twin-screw kneading extruder (co-rotating twin-screw kneading extruder HK-25D (41D), manufactured by Parker Corporation Co., Ltd.), at The screw speed was 150 rpm and the kneading temperature was 270°C (the measured resin temperature was 290°C) for kneading and granulation using a granulator to obtain the aromas of Zn(TBZ)(BDC) (Example 1) and TBZ. Particles of the polycarbonate resin composition. After drying the above-mentioned pellets and the pellets without the addition of the chemical agent (BL) at 100°C, the pellets were respectively heated at a cylinder temperature of 270-290°C and a mold using an injection molding machine (small electric injection molding machine SE18DUZ, manufactured by Sumitomo Heavy Industries, Ltd.). Injection molding was performed under the conditions of a temperature of 80° C. and a molding cycle of 40 seconds or 300 seconds, and a flat test piece with a thickness of 40×40×2 mm was produced. Using the obtained flat test piece, a weathering treatment (ultraviolet intensity: 180 W/m ² ; treatment time: 100 h) was performed by a super xenon weathering tester. The results are shown in FIG. 6 . Compared to the resin kneaded with TBZ, the resin kneaded with Zn(TBZ)(BDC) suppressed yellowing.

(Antibacterial test using a flat plate test piece) An antibacterial test was performed using the flat plate test piece obtained in the above weathering test (without weathering treatment by a super xenon weathering tester). According to JIS-Z-2801, Escherichia coli and Staphylococcus aureus were used as test bacteria. Place the test piece in a plastic petri dish, use NB (Nutrient Broth, nutrient gravy) medium to dilute the test bacteria pre-cultured on ordinary agar medium to prepare a bacterial solution for inoculation, drop it on the sample, cover with a film, and use Incubate in a constant temperature and humidity chamber (35±1°C, 95% relative humidity). After 24 hours, the surface of the test piece and the membrane were washed out with SCDLP (Soya Casein Digest Lecithin Polysorbate) medium. The number of bacteria per 1 ml of the eluted solution was calculated by the agar plate culture method using ordinary agar medium, and the number of bacteria per 1 cm ² of the sample was obtained. The antibacterial test results are shown in Table 4. With respect to BL (blank sample), the antibacterial activity value of Zn(TBZ)(BDC) was 2 or more, and the antibacterial effect was confirmed.

[Table 4] sample Escherichia coli Staphylococcus aureus Number of living bacteria (cell/cm ² ) logarithm of bacteria Antibacterial activity value Number of living bacteria (cell/cm ² ) logarithm of bacteria Antibacterial activity value BL (blank sample) 1.1E+06 60 2.1E+04 4.3 Zn(TBZ)(BDC) 4.4E+00 0.6 5.4 4.1E+01 1.6 2.7 E+06 means × 10 ⁶ antibacterial activity value = log value of BL (blank sample) - log value of Zn(TBZ) (BDC)

Even if it is kneaded into a polycarbonate resin that needs to be molded at a high temperature, Zn(TBZ)(BDC) is effective because of its excellent heat resistance.

(Anti-mold test using a flat plate test piece) The mildew-proof test was performed using the flat-plate test piece obtained in the above-mentioned weather resistance test (after the weather resistance treatment was performed by a super xenon weather resistance tester). The anti-mold test is in accordance with the test B method of plastic products in Annex A of JIS Z 2911:2018. Each test piece was placed on an inorganic salt agar medium supplemented with glucose, sprayed with the mixed spore suspension of Nigella nigra, Penicillium pinophilus, Paecilomycetes, Trichoderma viridans, and Chaetomium globosa, and cultured at 29°C. After a certain period of time, the mold production on the sample was evaluated on a 6-point scale (0: no mold production was observed with the naked eye and under a microscope to 5: the entire sample could be confirmed with the naked eye) on the basis of the following criteria. Table 5 shows the results of the antifungal test using the flat test piece subjected to the weathering treatment by the super xenon weathering tester. Four weeks after the start of the test, compared with the polycarbonate resin with TBZ kneaded, the case where Zn(TBZ)(BDC) was kneaded inhibited the generation of mold.

[table 5] sample 1 week Two weeks 3 weeks 4 weeks BL 3 4 4 4 TBZ 3 3 4 4 Zn(TBZ)(BDC) 1 2 2 2

It was shown that Zn(TBZ)(BDC) is also excellent in weather resistance.

The complex macromolecule containing tiabiline, terephthalic acid and zinc reduces the color change caused by light or heat, and is not easily decomposed even if high heat is applied, and is not easily leached into water, and has excellent weather resistance. It can be widely used for pest control such as mildew-proof or antibacterial use.

(Antivirus test using hard coat film) A hard coat was produced, and the efficacy against phage Qβ was confirmed.

The coating film was produced using an automatic coating device (PI-1210 manufactured by TESTER SANGYO), and a biaxially stretched polyester (PET) film (Lumirror(R) film, T60 transparent, 250 μm, 148×210 manufactured by Toray Corporation) mm) coated with about 3 mL of coating material solution (ethanol 81.06, KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) 8.74, ORGANO SILICA SOL IPA-ST (manufactured by Nissan Chemical Industries, Ltd.) 3.5, 2-methyl-4' -(Methylthio)-2-𠰌olinyl Propiophenone 0.2, Aluminum Acetylacetonate 1.5, Zn(TBZ)(BDC) 5 (unit: Wt%)). Then, it dried for 1 minute in the thermostatic bath of 100 degreeC, and it hardened|cured by the light source device (made by EYE GRAPHICS company) for ultraviolet hardening.

Antiviral test According to JIS R 1756:2020 "Precision Ceramics - Visible Light Responsive Photocatalyst Materials Antiviral Test Method - Method Using Bacteriophage Qβ", the antiviral test of the prepared hard coat was carried out. However, the test piece (hard coat film) inoculated with the test liquid was not irradiated with light, but was left still in a dark place. Phage infectivity titers were determined using E. coli after treating the phages on the hardcoat and standing for 4 hours.

As a result, the antiviral activity value of the hard coat film prepared by adding Zn(TBZ)(BDC) was higher than that of the hard coat film prepared by adding TBZ instead of Zn(TBZ)(BDC), and excellent activity was observed. .

FIG. 1 is a graph showing a powder X-ray diffraction (XRD) pattern of the crystal obtained in Example 1. FIG. 2 is a diagram showing a partial structure of a molecular model prepared for the crystal obtained in Example 1 based on X-ray structural analysis. 3 is a diagram showing a partial structure of a molecular model prepared for the crystal obtained in Example 2 based on X-ray structural analysis. 4 is a graph showing powder X-ray diffraction (XRD) patterns of the crystals obtained in Example 2 and the crystals after solvent removal. 5 is a graph showing the crystals obtained in Examples 1 and 2 and the measurement results obtained by TG-DSC (thermal analyzer) of Comparative Example (TBZ). FIG. 6 is a photograph of the result of a weathering test after kneading a polycarbonate resin with the crystal obtained in Example 1 and a comparative example (TBZ). FIG. 7 is a diagram showing the result of measurement with an infrared spectrophotometer (FT-IR) of the crystal obtained in Example 1, and a part thereof is shown enlarged. FIG. 8 is a graph showing the result of 13C-CPMAS-NMR measurement of the crystal obtained in Example 1. FIG. (a) is the overall spectrum, (b) is the amplified spectrum, (top) represents the Zn(TBZ)(BDC) obtained by Example 1, (middle) represents the raw material BDC, and (bottom) represents the raw material TBZ.

Claims (8)

A coordination macromolecule containing tiabiline (TBZ), terephthalic acid (BDC) and zinc (Zn). The coordination polymer of claim 1, which is a compound represented by the formula (I) or its solvent adduct, [Zn _a (TBZ) _b (BDC) _c R _d ] _n (I) (wherein, R represents the counter anion of zinc ion; a, b and c represent an integer of 1 or more, d represents an integer of 0 or more; n is the aggregate number of structural units represented by Zn _a (TBZ) _b (BDC) _c R _d , and not particularly limited). The coordination polymer according to claim 1 or 2, which is represented by [Zn(TBZ)(BDC)] _n or [Zn ₄ (TBZ) ₂ (BDC) ₃ ] _n (in the equation, n is Zn( The number of sets of structural units represented by TBZ) (BDC) or Zn ₄ (TBZ) ₂ (BDC) ₃ is not particularly limited). A pest control composition comprising the coordination polymer according to any one of claims 1 to 3. 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. The pest control composition according to claim 4 or 5, which is used as a microbial contamination control agent for industrial products. The pest control composition of claim 6, wherein the pest control composition is a resin composition. The pest control composition of claim 6, wherein the pest control composition is fiber or yarn.

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