WO2022113972A1 - Coordination polymer and composition containing same for pest control - Google Patents

Coordination polymer and composition containing same for pest control Download PDF

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Publication number
WO2022113972A1
WO2022113972A1 PCT/JP2021/042908 JP2021042908W WO2022113972A1 WO 2022113972 A1 WO2022113972 A1 WO 2022113972A1 JP 2021042908 W JP2021042908 W JP 2021042908W WO 2022113972 A1 WO2022113972 A1 WO 2022113972A1
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tbz
bdc
acid
coordination polymer
pest control
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PCT/JP2021/042908
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French (fr)
Japanese (ja)
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真生 箕浦
大哉 小林
陽 濱川
友紀 山口
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日本曹達株式会社
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Priority to JP2022565353A priority Critical patent/JPWO2022113972A1/ja
Publication of WO2022113972A1 publication Critical patent/WO2022113972A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/14—Monocyclic dicarboxylic acids
    • C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
    • C07C63/26—1,4 - Benzenedicarboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc compounds

Definitions

  • the present invention relates to a coordination polymer containing thiabendazole. More specifically, the present invention relates to a coordination polymer containing thiabendazole, terephthalic acid and zinc, and a composition for controlling pests containing the same.
  • This application claims priority to Japanese Patent Application No. 2020-196167 filed on November 26, 2020, the contents of which are incorporated herein by reference.
  • Thiabendazole is widely used as a fungicide, a fungicide, a preservative, an anthelmintic and the like.
  • Patent Documents 1 to 4 describe that thiabendazole is used for wood products, paper, PVC and the like for these purposes.
  • Thiabendazole itself has some stability, but it is decomposed by light (ultraviolet rays), colored, and decomposed by heat (disappeared by high heat). By making various complexes, such decomposition and disappearance may be suppressed, that is, the physical stability may be improved. However, even if the complex itself is colored or the complex itself is white, it may be colored by light or heat.
  • Non-Patent Documents 1 and 2 describe the crystal structure, the polyvalent carboxylic acid is terephthalic acid, the color change due to light or heat is reduced, and it is difficult to decompose even when high heat is applied. There is no description indicating that. Further, there is no description that it has excellent weather resistance and can be preferably used for biocide applications.
  • An object of the present invention is to provide a pest control composition containing thiabendazole, which reduces color change due to light or heat, is difficult to decompose even when exposed to high heat, and suppresses water loss.
  • the present inventors have used a coordination polymer containing thiabendazole, terephthalic acid and zinc, which is harmful to contain thiabendazole which is difficult to decompose even under high heat. It has been found that a composition for biological control can be provided, and the present invention has been completed.
  • the present invention includes the following aspects.
  • N is represented by Zn a (TBZ) b (BDC) c R d . It is the number of sets of constituent units to be formed, and is not particularly limited.)
  • the coordination polymer according to (1) which is a compound represented by (1) or a solvent adduct thereof.
  • n Zn (TBZ) (BDC) or Zn 4 (TBZ) 2 ( BDC)
  • the coordination polymer according to (1) or (2) which is the number of sets of structural units represented by 3 and is not particularly limited).
  • the pest control composition according to (4) or (5) which is used as a microbial contamination control agent for industrial products.
  • the pest control composition according to (6), wherein the pest control composition is a resin composition.
  • the pest control composition according to (6), wherein the pest control composition is a fiber or a thread.
  • the thiobendazole-containing coordination polymer according to the present invention is unlikely to change in color due to light or heat, is not easily decomposed even when exposed to high heat, and is not easily leached into water. It is especially useful in fields where high heat is applied and in situations where there are many opportunities to come into contact with water.
  • FIG. It is a figure which shows the powder X-ray diffraction (XRD) pattern of the crystal obtained in Example 1.
  • FIG. It is a figure which shows the partial structure of the molecular model prepared based on the X-ray structure analysis about the crystal obtained in Example 1.
  • FIG. It is a figure which shows the partial structure of the molecular model prepared based on the X-ray structure analysis about the crystal obtained in Example 2.
  • FIG. It is a figure which shows the powder X-ray-diffraction (XRD) pattern of the crystal obtained in Example 2 and the crystal after solvent removal.
  • TG-DSC thermal analyzer
  • FIG. (A) is the whole, (b) is the expanded spectrum, (top) is the Zn (TBZ) (BDC) obtained in Example 1, (middle) is the raw material BDC, and (bottom) is the raw material TBZ. Is shown.
  • the pest control composition of the present invention contains a coordination polymer containing thiabendazole, terephthalic acid and zinc.
  • Coordination polymer containing thiabendazole A coordination polymer containing thiabendazole, terephthalic acid and zinc (hereinafter referred to as "coordination polymer containing thiabendazole") may have a different polymer structure depending on the zinc species. However, all of them are excellent as compositions for controlling harmful organisms.
  • Coordination polymer is a complex having a continuous structure consisting of a polydentate ligand and a metal ion.
  • a coordination polymer having a continuous (-MLML-) structure can be produced from a bidentate ligand L and a bidentate metal ion M. In the coordination polymer, the metal ion is located in the main chain.
  • a coordination polymer having a different dimensional structure can be obtained depending on the type of zinc salt, but the structure of the coordination polymer is not particularly limited, and any structure may be affected by light or heat. It is possible to obtain a pest control composition containing thiabendazole, which has reduced color change, is less likely to be decomposed even when subjected to high heat, and has suppressed water loss.
  • the coordination polymer of the present invention has the following formula (I). [Zn a (TBZ) b (BDC) c R d ] n (I)
  • Each structural unit represented by Zn a (TBZ) b (BDC) c R d is connected by a coordinate bond. It may be a solvent adduct in which the solvent is incorporated into the coordination polymer.
  • TBZ represents tiabendazole
  • BDC represents terephthalic acid
  • R represents the counter anion of zinc ion.
  • the counter anion is an anion moiety of a zinc compound, and examples thereof include halogeno 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 indicate an integer of 1 or more, specifically, an integer in the range of 1 to 50, 1 to 10, 1 to 5, etc.
  • d is an integer of 0 or more. Specifically, it indicates an integer in the range of 0 to 50, 0 to 10, 0 to 5, and the like.
  • n is the number of sets 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 achieved.
  • coordination polymers having constituent units such as Zn (TBZ) (BDC) and Zn 4 (TBZ) 2 (BDC) 3.6DMF can be mentioned.
  • DMF indicates the solvent N, N-dimethylformamide.
  • Zn1 Zn 4 (TBZ) 2 (BDC) 3.6 DMF
  • BDC Zn 4 (TBZ) 2
  • Zn2 coordination number 5
  • the N atom and the O atom in the BDC are coordinated and bonded to the zinc ions (Zn1 and Zn2) of other constituent units, and are connected in a network, resulting in the formation of one-dimensional channel vacancies.
  • Six DMFs, which are solvents, are incorporated into each structural unit.
  • Thiabendazole is a compound represented by the following formula and is a well-known compound as a bactericidal agent or the like.
  • Terephthalic acid is a compound represented by the following formula.
  • the zinc salt is a divalent inorganic or organic zinc salt.
  • the inorganic salt include salts of inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; and halides such as chlorides, bromides and iodides.
  • 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. Of these, nitrates, acetates, sulfates, chlorides, bromates, iodides, and lactates are preferred. These zinc salts may be used alone or in combination of two or more.
  • the solvent used for the synthesis is not particularly limited, but an organic solvent, water or a mixed solvent thereof can be used.
  • the solvent one kind alone or two or more kinds of mixed solvents can be used.
  • the organic solvent is not particularly limited, but specifically, 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.
  • Hydrocarbons such as methylene chloride and chloroform; acetone, ethyl acetate, acetonitrile, N, N-dimethylformamide (DMF), N, N-diethylformamide, N, N-dimethylacetamide and the like.
  • N, N-dimethylformamide it is preferable to use N, N-dimethylformamide.
  • These solvents may remain in the coordination polymer as long as they do not interfere with the purpose of controlling pests.
  • the molar concentration of the zinc salt in the solvent is preferably 0.005 to 5 mol / L, more preferably 0.01 to 2 mol / L.
  • the molar concentration of terephthalic acid is preferably 0.001 to 5 mol / L, more preferably 0.005 to 2 mol / L.
  • the molar concentration of thiabendazole is preferably 0.001 to 5 mol / L, more preferably 0.005 to 2 mol / L.
  • the thiabendazole-containing coordination polymer may be obtained only by mixing zinc salt, terephthalic acid and thiabendazole, but 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 exhibiting the above-mentioned predetermined characteristics can be obtained, but is preferably in the range of room temperature to 200 ° C. When heating, it is preferably 100 to 150 ° C.
  • the reaction time of this production method is not particularly limited as long as a coordination polymer exhibiting the above-mentioned predetermined characteristics can be obtained, but 1 hour or more is preferable, and 24 hours or more is more preferable in terms of better yield of the product. .. In the case of room temperature, it is preferable that the heating time is 24 hours or more, and the heating time in the heating step is 6 hours or more.
  • the procedure of this production method is not particularly limited as long as a coordination polymer exhibiting the above-mentioned predetermined characteristics is obtained, but for example, a method of mixing and heating thiabendazole, terephthalic acid and a zinc salt in the presence of a solvent is preferable. Can be mentioned.
  • the mixing method of the reaction substrate is not particularly limited, and a known method can be adopted.
  • the order in which each component is added is not particularly limited, and the above components may be added to the reaction vessel at the same time or may be added in order.
  • the product and the solvent can be easily separated by a separation method such as filtration or centrifugation.
  • the product prepared in the above step can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a separation means combining these. It is preferable that after filtering, the material is thoroughly washed with a solvent in which the raw materials terephthalic acid and zinc salt are dissolved, and vacuum dried at 100 ° C to 150 ° C.
  • the present solvent for example, the same solvent as that used for the synthesis can be used.
  • the structure, composition, and performance of the product can be confirmed by using a general method.
  • X-ray diffraction measurement confirmation of crystal structure
  • 13C-CPMAS-NMR measurement composition analysis of product
  • thermal analysis measurement of heat resistance
  • X-ray diffraction measurement and 13C-CPMAS-NMR are measured at room temperature as they are, and thermal analysis is measured by heating the powder in air from room temperature to 1000 ° C.
  • the pest control composition of the present invention may contain only the above components, but may also 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 use of the pest control composition, the required performance and the like. Examples of the resin include thermoplastic resins and heat or photocurable resins. These may be used alone or in combination of two or more.
  • thermoplastic resin used in the present invention is not particularly limited, but specifically, a styrene resin, an acrylic resin, a vinyl acetate resin, an acrylonitrile copolymer, a polyphenylene oxide resin (PPO), and a polysulfone resin (.
  • PSF polyether sulfone
  • PAR polyarylate
  • PES polyetherimide
  • PEI polyamideimide
  • PAI polyimide
  • PI polymethylmethacrylate
  • AS resin acrylonitrile-styrene copolymer
  • AS resin Acrylonitrile-styrene-N-substituted maleimide ternary copolymer
  • ABS resin Acrylonitrile-styrene-N-substituted maleimide ternary copolymer
  • ABS resin Acrylonitrile-styrene-N-substituted maleimide ternary copolymer
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • SVC polyvinyl chloride
  • polyethylene polycarbonate resin
  • PC polybutylene terephthalate resin
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • PET polyethylene
  • thermal or photocurable resin used in the present invention is not particularly limited, but is a monomer having a vinyl group, a (meth) acryloyl group, an epoxy group, and an oxetanyl group, a prepolymer, an oligomer, and a polymer. Etc. can be used. Above all, it is preferable to use a polyfunctional resin.
  • "(meth) acryloyl group” means "acryloyl group” and / or "methacryloyl group”.
  • a polyfunctional group or a monofunctional (meth) acrylate monomer or an acrylate oligomer can be used.
  • the 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.
  • the "(meth) acrylate group” means an "acrylate group” and / or a "methacrylate group”.
  • the acrylate monomer of the polyfunctional group is a monomer having two or more (meth) acrylate groups in the molecule, preferably 2 to 6, for example, trimethylolpropane diacrylate, neopentyl glycol diacrylate, and the like.
  • examples of the acrylate oligomer include epoxy acrylate oligomer, polyester polyacrylate oligomer, urethane acrylate oligomer and the like.
  • polyfunctional or monofunctional (meth) acrylate monomers or oligomers can be used alone or in combination of two or more.
  • Specific examples thereof include silicon resin, silicone resin, acrylic silicone resin, epoxy resin, polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, silicon resin and diallyl phthalate resin.
  • composition for controlling pests of the present invention comprises a coordination polymer composed of thiabendazole, terephthalic acid and zinc, or a solvent capable of dispersing or dissolving a mixture of the coordination polymer and a resin or the like. It may be included.
  • the solvent is not particularly limited, but is water; organic acids such as formic acid, acetic acid, lactic acid, oxalic acid, citric acid, and benzoic acid; alcohols such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, and n-butanol; ethanolamine.
  • Dimethylamine amines such as pyridine; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; ketones such as acetone, methylethylketone, methylisobutylketone, cyclohexanone, acetylacetone; ethers such as diethyl ether, dimethylether, tetrahydrofuran Classes; 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; dichloromethane, Halogenized hydrocarbons such as carbon tetrachloride, chloroform and chilichloroethylene; acetonitrile; mineral oils, synthetic hydrocarbon oils, synthetic hydrocarbon
  • compositions of the present invention can be further added to the pest control composition of the present invention as long as the effects of the present invention are not impaired.
  • Such components include flame retardants, heat stabilizers, antioxidants, lubricants, antibacterial agents, UV inhibitors, colorants, mold release agents, heat shields, dispersants, surfactants, pH regulators, etc.
  • Antimicrobial components such as defoaming agents, rust preventives, viscosity regulators, metal sequestering agents, friction modifiers, other antibacterial components, bactericidal components, antiviral components, antifungal components, antiseptic components, insecticides, Examples include herbicides and plant growth regulators. These can be used in combination of two or more.
  • the flame retardant is not particularly limited, but for example, a halogen-based flame retardant such as chlorine-based or bromine-based; an organic-based flame retardant such as a phosphorus-based flame retardant; a nitrogen-containing flame retardant, an antimony-based flame retardant, or a metal hydroxide-based flame retardant.
  • a halogen-based flame retardant such as chlorine-based or bromine-based
  • an organic-based flame retardant such as a phosphorus-based flame retardant
  • a nitrogen-containing flame retardant such as a phosphorus-based flame retardant
  • an antimony-based flame retardant such as antimony-based flame retardant
  • a metal hydroxide-based flame retardant such as inorganic flame retardants, boron-based flame retardants (boric acid flame retardants), and red phosphorus flame retardants can be used. These can be used in combination of two or more.
  • the heat stabilizer is not particularly limited, and examples thereof include phosphorus-based heat stabilizers such as phosphite ester and phosphoric acid ester.
  • phosphorous acid ester include triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonylphosphite, tridecylphosphite, and trioctyl.
  • Phosphite Trioctadecylphosphite, Distearylpentaerythritol diphosphite, Tricyclohexylphosphite, Monobutyldiphenylphosphite, Monooctyldiphenylphosphite, Distearylpentaerythritol 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) ) Octylphosphite] and other phosphorous acid triesters, diesters, monoesters and the like.
  • Phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, and tetrakis (2,4-di-).
  • tert-butylphenyl) -4,4-diphenylene phosphonite and the like can be mentioned.
  • the antioxidant is not particularly limited, and examples thereof include a phenol-based antioxidant, a phosphorus-based antioxidant, a phosphite-based antioxidant, and a thiourea-based antioxidant.
  • the lubricant is not particularly limited, and examples thereof include higher fatty acids, ester waxes, polyethylene waxes, and metal soaps.
  • the antistatic agent is not particularly limited, and examples thereof include fatty acid amines, fatty acid alcohols, fatty acid esters, fatty acid amides, and sulfonic acid compounds.
  • the ultraviolet inhibitor is not particularly limited, and examples thereof include benzotriazole compounds such as salicylic acid derivative compounds, benzophenone compounds, and benzotriazole derivatives, and cyanoacrylate compounds.
  • the colorant is not particularly limited, and examples thereof include organic pigments, inorganic pigments, dyes, and brighteners.
  • organic pigments include phthalocyanine-based, benzimidazolone-based, azo-based, azomethine-azo-based, azomethine-based, anthracinone-based, perinone-perylene-based, indigo-thioindigo-based, dioxazine-based, quinacridone-based, isoindrin-based, and iso.
  • examples thereof include indolinone pigments and carbon black pigments
  • examples of the inorganic pigments include extender pigments, titanium oxide pigments, iron oxide pigments and spinnel pigments.
  • insoluble azo pigments such as toluidin red, toluidin maroon, hanza yellow, benzidine yellow, pyrazolon red, soluble azo pigments such as litol red, heliobordeaux, pigment scarlet, permanent red 2B, phthalocyanine blue, phthalocyanine green and the like.
  • pigments such as thioindigo-based, condensed azo-based, benzimidazolone-based, quinophthalone yellow, nickel azo yellow, perinone orange, anthlon orange, dianthraquinonyl red, and dioxazine violet can be used.
  • the dye for example, conventionally known dyes such as direct dyes, basic dyes, cationic dyes, acidic dyes, medium dyes, acidic medium dyes, sulfide dyes, naphthol dyes, disperse dyes, and reactive dyes can be used.
  • the glittering agent include aluminum paste, mica, and flaky iron oxide.
  • the release agent is not particularly limited, and examples thereof include an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000, and a polysiloxane-based silicone oil. can.
  • examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids.
  • the aliphatic carboxylic acid also includes an alicyclic carboxylic acid.
  • aliphatic carboxylic acid examples include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, araquinic acid, bechenic acid, lignoseric acid, cellotic acid, melissic acid, tetrariacontanic acid, montanic acid and adipic acid. , Azelaic acid and the like.
  • the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol the same one as the above-mentioned aliphatic carboxylic acid 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.
  • the aliphatic term also contains an alicyclic compound.
  • 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, and dipentaerythritol. And so on.
  • These ester compounds of the aliphatic carboxylic acid and the alcohol may contain the aliphatic carboxylic acid and / or the alcohol as impurities, or may be a mixture of a plurality of compounds.
  • esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monosteer.
  • esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monosteer.
  • examples thereof include rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaery
  • Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fishertroph wax, and ⁇ -olefin oligomer having 3 to 12 carbon atoms.
  • the aliphatic hydrocarbon also includes an alicyclic hydrocarbon.
  • these hydrocarbon compounds may be partially oxidized.
  • Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. These may be used alone or in combination of two or more.
  • the heat-shielding agent is not particularly limited as long as it is generally used by those skilled in the art, such as an infrared (near-infrared) shielding agent, an absorbent dye, and a reflective pigment (heat-shielding pigment).
  • the dispersant is an additive used to uniformly disperse solid particles such as inorganic and organic pigments in a medium to prepare a stable dispersion. Although not particularly limited as long as the object of particle dispersion can be achieved, various surfactants and the like can be used, for example.
  • surfactant examples include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and the like.
  • nonionic surfactant examples include polyoxyalkylene alkylphenyl ether, polyoxyalkylene arylphenyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene vegetable oil and the like.
  • anionic surfactant examples include alkylbenzene sulfonates, alkylnaphthalene sulfonates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkyl phenyl ether sulfates. , Dialkylsulfosuccinate and the like.
  • the cationic surfactant include aliphatic amine salts and quaternary ammonium salts.
  • amphoteric surfactant examples include an alkyl betaine type surfactant, an amidopropyl betaine type surfactant, an imidazolinium betaine type surfactant, a sulfobetaine type surfactant, a phosphobetaine type surfactant and the like. .. These surfactants can be used alone or in combination of two or more.
  • 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 salts thereof, and inorganic acids such as phosphoric acid, polyphosphoric acid and boric acid and salts thereof. Be done.
  • the defoaming agent is not particularly limited, and examples thereof include mineral oil-based, silicone-based, polyether-based, fluoroalkyl ether, and polyalkylene glycol-based defoaming agents.
  • the rust preventive is not particularly limited, but for example, metal sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, organic subphosphate ester, organic phosphate ester, organic sulfonic acid metal salt, organic phosphate metal salt, alkenyl succinic acid.
  • metal sulfonate alkylbenzene sulfonate, dinonylnaphthalene sulfonate, organic subphosphate ester, organic phosphate ester, organic sulfonic acid metal salt, organic phosphate metal salt, alkenyl succinic acid.
  • esters include esters, polyhydric alcohol esters, benzotriazole-based compounds and the like.
  • the viscosity adjusting agent is not particularly limited, and examples thereof include xanthan gum, carboxymethyl cellulose, hydroxyethyl cellulose, gum arabic, gellan gum, pullulan and the like.
  • the metal sequestering agent is not particularly limited, and is, for example, ethylenediamine tetraacetic acid or a salt thereof, nitrilotriacetic acid or a salt thereof, diethylenetriaminepentacetic acid or a salt thereof, hydroxyethylethylenediaminetriacetic acid or a salt thereof, triethylenetetraminehexacetic acid or a salt thereof.
  • salt 1,3-propanediaminetetraacetic acid or a salt thereof, 1,3-diamino-2-hydroxypropanetetraacetic acid or a salt thereof, 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof, hydroxyethyliminodiacetic acid
  • examples thereof include dihydroxyethylglycine or a salt thereof, glycol ether diaminetetraacetic acid or a salt thereof, dicarboxymethyl glutamate or a salt thereof, nitrilotrismethylene phosphate or a salt thereof, and the like.
  • the friction modifier is not particularly limited, and examples thereof include fatty acids, fatty acid esters, and alcohols.
  • the active ingredient used may be a liquid or a solid, 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 plurality of kinds of components can be used in combination.
  • antibacterial component examples include benzimidazole compounds such as benomil, carbendazim, thiabendazole, and thiophanatemethyl; phenylcarbamate compounds such as dietofencarb; Dicarboxyimide compounds; azole compounds such as triflumizole, hexaconazole, diniconazole, epoxyconazole, tebuconazole, diphenoconazole, cyproconazole, propiconazole, flusilazole, triazimephon, methconazole, microbutanyl, imazalyl, triphorin.
  • Acylalanine compounds such as metalaxyl; Carboxamide compounds such as flametopyl, mepronyl, flutranyl and trifluzamide; Organic phosphorus compounds such as turquophosmethyl, fosetylaluminum and pyrazophos; Anilinopyrimidine compounds such as pyrimesanyl, mepanipylim and cyprodinyl Cyanopyrrole compounds such as fludioxonyl and fenpicronyl; Antibiotics such as blastsaidin S, casgamicin, polyoxin, and varydamycin; Compounds; iminoctazine acetate, iminoctazine albesilate, penflufen, chlorotalonyl, manzeb, captan, folpet, oxine copper, basic copper chloride, tricyclazole, pyrochyron, probenazole, fusalide, simoxanyl, dimethomorph, CGA245704,
  • haloalkylthio compounds such as N- (fluorodichloromethylthio) -phthalimide, N- (fluorodichloromethylthio) -N, N'-dimethyl-N-phenyl-sulfamide, ⁇ -t-butyl- ⁇ (p-chlorophenyl) Ethyl) -1H-1,2,4-triazole-1-ethanol (commonly known as tebuconazole) and other triazole compounds, 1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazole- 3 (2H) -one, 2-methyl-4,5-trimethylethylene-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3 -On, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-
  • Parachloromethacresol 4-Chloro-3,5-xylenol, Triazine-1,3,5 (2H, 4H, 6H) -Triethanol, Streptomycin, Diuron (DCMU), Dimulon, Metobenzlon, Cumyllon, Nicosulfron, Linuron, Sibutrin, Telbutrin , Simazine, Atlasin, Propazine, Cyanazine, Dimetamethrin, Promethrin, Butraline, Benflularin, Prodiamine, Benzophenap, Pyrflufen-ethyl, Biphenox, Bromobutide, Bromoxinyl, Propanyl, Diflufenican, Mephenacet, Chromeprop, Dicrosslam, Dithiopyl, Isoxaben Pyributycarb, pyriminobac-methyl, oxadiazone, oryzarin, oxadiargyl, fluthi
  • the pest control composition of the present invention can also be used as a composition together with an insecticide, a herbicide, a plant growth regulator and the like.
  • These components can be used without particular limitation.
  • the active ingredient used may be a liquid or a solid, 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 plurality of kinds of components can be used in combination. A specific example is shown below.
  • Insecticides include cifluthrin, cypermethrin, deltamethrin, phenpropatrin, fenvalerate, esphenvalerate, tralomethrin, acrinathrin, bifentrin, resmethrin, tetramethrin, tefurthrin, etofenprox, ciphenotrin, permethrin, plaretrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, Pyrethroid compounds of , Dimethylbinphos, Hosalon, Chlorpyriphos, Chlorpyriphosmethyl, Pyridafenthion, Kinalphos, Metidathione, Metamidhos, Dimethate, Fermotion, Adinphosethyl, Adinphosmethyl, Salithion, Fenitrothione and other organic phosphorus compounds; , Fluphenoxuron
  • triazine compounds such as atrazine and methrividine
  • urea compounds such as fluometurone and isoproturon
  • hydroxybenzonitrile compounds such as bromoxynyl and ioxynyl
  • 2,6-dinitroaniline compounds such as pendimesarin and triflularin.
  • Allyloxy alkanoic acid compounds such as 2,4-D, dicamba, fluroxypyll, mecoprop
  • sulfonylurea compounds such as benzulflonmethyl, meturfuronmethyl, nicosulfone, primisulfuronmethyl, cyclosulfamron
  • imazapill Imazakin, imidazolinone compounds such as imazetapill
  • Examples thereof include butyl, difluphenican, norflurazone, isoxaflutol, glufosinate anmnium salt, glyphosate, bentazone, benocarb, mephenacet, compound, fluthamide and the like.
  • plant growth regulators include maleic hydrazide, chlormecut, etefon, gibberellin, mepicat chloride, tidiazulone, inabenfide, paclobutrazol, and uniconazole.
  • insect repellent include 1S, 3R, 4R, 6R-curan-3,4-diol, dipropyl 2,5-pyridinedicarboxylate and the like.
  • Polymer initiator When a heat or photocurable resin is used as the resin, a polymerization initiator may be contained. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator.
  • photopolymerization initiator examples include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [DaroCure 2959: manufactured by Merck], ⁇ -hydroxy- ⁇ , ⁇ '. -Acetophenone-based initiators such as dimethylacetophenone [Darocure 1173: manufactured by Merck], methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651]; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether. Initiators; other examples include halogenated ketones, acylphosphinoxides, acylphosphonates and the like.
  • Thermal polymerization initiators that can be used in the present invention include azo-based initiators and peroxide-based initiators.
  • azo-based initiator examples include azobis (isobutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), and 2,2'-azobis ⁇ 2-methyl-N- [1,1. -Bis (hydroxymethyl) ethyl] propionamide ⁇ , 2, 2'-azobis [2-methyl-N- (2-heroxyethyl) propionamide], 2, 2'-azobis [2- (hydroxymethyl) propionitrile ], 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (dimethyl isobutyrate), 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] Propionamide ⁇ and the like can be exemplified. Of these, azobis (iso
  • the peroxide-based initiator preferably has a half-life of 10 hours and a temperature of 80 ° C. or lower, which is relatively easily decomposed. It can be exemplified.
  • the peroxide-based initiator one that has a short thermal polymerization time and is stable as a reactive composition before polymerization can be appropriately selected.
  • Such a polymerization initiator is blended in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable resin. Preferably, it is blended in the range of 0.01 to 1 part by weight.
  • the pest control composition of the present invention can be used as it is by producing a thiabendazole-containing coordination polymer. If necessary, the thiabendazole-containing coordination polymer is prepared and then mixed with other components such as resin.
  • a mixing method a conventionally known method can be used for mixing, but for example, when a resin is used, it can be produced by melt-kneading. Specifically, a thermoplastic resin, a coordination polymer containing thiabendazole, and other additive components to be blended as necessary are weighed in a predetermined amount, mixed using various mixers such as a tumbler and a henschel mixer, and then Banbury.
  • Examples thereof include a method of melt-kneading using a mixer, a roll, a plastic pender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader and the like.
  • 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 products).
  • a conventionally known method of molding a molded product from a thermoplastic resin material can be applied without limitation.
  • 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 changed as appropriate depending on what is mixed.
  • the mixing amount of the resin is not particularly limited, but is preferably 1 to 1000 parts by weight with respect to 1 part by weight of the coordination polymer containing thiabendazole. It is preferably 1 to 300 parts by weight.
  • the mixing amount of the solvent is not particularly limited, but is preferably 1 to 1000 parts by weight with respect to 1 part by weight of the coordination polymer containing thiabendazole. It is preferably 2 to 100 parts by weight.
  • the pest control composition containing the resin according to the present invention and its molded product exhibit antimicrobial activity such as antibacterial activity, antibacterial activity, and antiviral activity. Therefore, applications that require anti-microbial properties, such as water-related products such as spray containers and kitchen utensils, food packaging materials, cover cloths, household products such as garbage covers; sanitary products such as rubber footwear; bathrooms.
  • the pest control composition of the present invention has a composition with at least one selected from paints, pigments, inks, fibers, pulps, rubbers, latexes, adhesives, films, formulations, ceramic materials, and metalworking oils. It can also be preferably used as a product.
  • 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 fiber ⁇ Synthetic fiber (polyamide-based such as nylon and aramid fiber; 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 fiber, Polyacrylonitrile-based such as modacryl fiber; Polyester-based such as polyethylene fiber, polypropylene fiber, and polystyrene fiber; Polyurethane-based such as polyurethane; Polyclaral-based such as polyclaral; Polyfluoroethylene-based such as fluorine fiber; Polyester ester type such as success; Polylactic acid type such as polylactic acid fiber; Polyalkylene paraoxybenzoate type such as benzoate; Polytetrafluoroethylene type; Polyblue vinyli
  • examples of the form of the target textile product include threads, strings, ropes, fabrics (woven fabrics, knitted fabrics, non-woven fabrics) and the like.
  • Specific examples include linen items such as sheets, pillowcases and towels; various clothing items such as pajamas, white clothes, aprons, hats, uniforms and uniforms; fashion accessories such as bags and shoes; car seats, chairs, strollers, etc.
  • Seats and their seat covers Interior materials such as curtains and wallpaper; Filters such as air conditioning filters and vacuum cleaner filters; Outdoor products such as tents and sleeping bags; Sanitary products such as masks; Seats for refrigerators, freezer covers, etc. , Can be widely used for household goods and industrial materials.
  • the pest control composition according to the present invention exhibits antimicrobial activity such as antibacterial activity, antibacterial activity, and antiviral activity. Therefore, any material that requires antimicrobial properties can be suitably used.
  • Example 1 [Zn (TBZ) (BDC)] n coordination polymer (hereinafter, simply referred to as “Zn (TBZ) (BDC)”)
  • Zn (TBZ) (BDC) n coordination polymer
  • the powder X-ray diffraction pattern of the obtained single crystal was measured by CuK ⁇ ray using the measuring device Bruker D2PHASER, the diffraction pattern as shown in FIG. 1 was obtained in the powder X-ray measurement from 5 ° to 50 °. Indicated.
  • FIG. 7 shows the measurement results of the crystal obtained in Example 1 by an infrared spectrophotometer (FT-IR).
  • FT-IR infrared spectrophotometer
  • Example 2 [Zn 4 (TBZ) 2 (BDC) 3.6DMF ] n coordination polymer (hereinafter, simply referred to as “Zn 4 (TBZ) 2 (BDC) 3.6DMF ”)
  • Zn 4 (TBZ) 2 (BDC) 3.6DMF n coordination polymer
  • each structural unit represented by Zn 4 (TBZ) 2 (BDC) 3.6 DMF is connected in a network to form a one-dimensional channel hole. It was confirmed that it is a coordination polymer having.
  • Zn 4 (TBZ) 2 (BDC) 3 ⁇ 6DMF means that 6 molecules of DMF per unit are incorporated into Zn 4 (TBZ) 2 (BDC) 3 pores.
  • Table 2 The spatial information in the X-ray structure analysis is shown in Table 2, and the molecular model is shown in FIG.
  • the sample Zn 4 (TBZ) 2 (BDC) 3.6 DMF was allowed to stand in an environment of 150 ° C. and dried under reduced pressure with a vacuum pump to remove the solvent (DMF).
  • the powder X-ray diffraction pattern was measured with CuK ⁇ rays using the measuring device Bruker D2PHASER. In the powder X-ray measurement from 5 ° to 50 °, the diffraction pattern as shown in FIG. 4 was shown. By removing the solvent, a slight difference was observed in the powder X-ray diffraction pattern.
  • Bacterial MIC test An inoculum of cultured bacteria (Escherichia coli, Staphylococcus aureus subsp.
  • each injection molding machine small electric injection molding machine SE18DUZ manufactured by Sumitomo Heavy Industries, Ltd.
  • a molding cycle of 40 seconds or 300 seconds to prepare a plate test piece having a thickness of 40 ⁇ 40 ⁇ 2 mm.
  • Antibacterial test using plate test piece An antibacterial test was performed using a plate test piece (without weather resistance treatment with a super xenon weather meter) obtained in the above weather resistance test. According to JIS-Z-2801, Escherichia coli and Staphylococcus aureus subsp. aureus was used. Place the test piece on a plastic petri dish, dilute the test bacteria pre-cultured on a normal agar medium with NB medium to obtain a bacterial solution for inoculation, drop it on the sample, cover it with a film, and place it in a constant temperature and humidity chamber (35 ⁇ 1). Cultivated at ° C. and relative humidity 95%).
  • Coordination polymers containing thiabendazole, terephthalic acid, and zinc have excellent weather resistance, with reduced color change due to light and heat, less decomposition even when exposed to high heat, and less leaching into water. be. It can be widely used for controlling harmful organisms such as antifungal and antibacterial applications.
  • Coating film creation Using an automatic coating device (PI-1210 manufactured by Tester Sangyo Co., Ltd.), a biaxially stretched polyester (PET) film manufactured by Toray Industries, Inc. (Lumirror (R) film T60 transparent 250 ⁇ m 148 ⁇ 210 mm) Coating material liquid (ethanol 81.06, KBM-503 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 8.74, organosilica sol IPA-ST (manufactured by Nissan Chemical Industry Co., Ltd.) 3.5, 2-methyl-4'-(methylthio) -2 -About 3 mL of morpholinopropiophenone 0.2, Aluminum acetylacetonate 1.5, Zn (TBZ) (BDC) 5 (unit: Wt%)) was applied. Then, it was dried in a constant temperature bath at 100 ° C. for 1 minute, and solidified by an ultraviolet curing optical source device (manufactured by Eye Graphics Co., Ltd.).
  • Antiviral test An anti-virus test was performed on the prepared hard coat coating film in accordance with JIS R 1756: 2020 "Fine Ceramics-Anti-virus test method for visible light responsive photocatalytic materials-Method using bacteriophage Q ⁇ ". However, the test piece (hard coat coating film) inoculated with the test solution was not irradiated with light, and was only allowed to stand in a dark place. The hardcourt coating was treated with bacteriophage and allowed to stand for 4 hours, and then the bacteriophage infectivity titer was measured using Escherichia coli.
  • the hard-coated coating film prepared by adding Zn (TBZ) (BDC) has antiviral activity as compared with the hard-coated coating film prepared by adding TBZ instead of Zn (TBZ) (BDC). The value was high and excellent activity was observed.

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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

配位高分子およびそれを含有する有害生物防除用組成物Coordination polymer and pest control composition containing it
　本発明は、チアベンダゾールを含有する配位高分子に関するものである。詳しくは、チアベンダゾール、テレフタル酸及び亜鉛を含有する配位高分子およびそれを含有する有害生物防除用組成物に関する。本願は、２０２０年１１月２６日に出願された日本国特許出願第２０２０－１９６１６７号に対し優先権を主張し、その内容をここに援用する。 The present invention relates to a coordination polymer containing thiabendazole. More specifically, the present invention relates to a coordination polymer containing thiabendazole, terephthalic acid and zinc, and a composition for controlling pests containing the same. This application claims priority to Japanese Patent Application No. 2020-196167 filed on November 26, 2020, the contents of which are incorporated herein by reference.
　チアベンダゾールは、殺菌剤、防カビ剤、防腐剤、駆虫剤等として、幅広く用いられている。例えば、特許文献１～４には、チアベンダゾールがこれらの目的で木材製品、紙、ＰＶＣ等に用いられることが記載されている。
　チアベンダゾール自体は、ある程度の安定性はあるが、光（紫外線）による分解や着色、熱による分解（高熱では消失）が生ずる。
　各種錯体化することでこうした分解や消失が抑制、即ち物性的に安定性が向上することもある。しかし、錯体自体が着色したものであったり、錯体自体が白色であっても、光や熱によって着色を起こすことがある。結果、組成物として用いる場合に、混合相手となる素材そのものの色・質感が失われるという問題があった。
　他方、チアベンダゾール、多価カルボン酸及び重金属イオンからなる配位高分子化合物が、非特許文献１及び２に記載されている。しかしながら、これらの文献には、結晶構造について記載されているが、多価カルボン酸がテレフタル酸であることや、光や熱による色調変化が軽減され、かつ、高熱をかけても分解しにくいものであることを示す記載がない。また、耐候性に優れ、バイオサイド用途に好ましく用いることができることについても、記載がない。 Thiabendazole is widely used as a fungicide, a fungicide, a preservative, an anthelmintic and the like. For example, Patent Documents 1 to 4 describe that thiabendazole is used for wood products, paper, PVC and the like for these purposes.
Thiabendazole itself has some stability, but it is decomposed by light (ultraviolet rays), colored, and decomposed by heat (disappeared by high heat).
By making various complexes, such decomposition and disappearance may be suppressed, that is, the physical stability may be improved. However, even if the complex itself is colored or 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 itself to be mixed is 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, the polyvalent carboxylic acid is terephthalic acid, the color change due to light or heat is reduced, and it is difficult to decompose even when high heat is applied. There is no description indicating that. Further, there is no description that it has excellent weather resistance and can be preferably used for biocide applications.
特開２０１７－１６５６９２号公報JP-A-2017-165692 特表２０１６－５３２７８８号公報Special Table 2016-532788 Gazette 特表２０１５－５１６３８２号公報Special Table 2015-516382 Gazette 特表２０１５－５１６３８１号公報Japanese Patent Publication No. 2015-516381
　本発明の目的は、光や熱による色調変化が軽減され、高熱をかけても分解しにくく、そして水溶脱が抑えられたチアベンダゾールを含有する有害生物防除用組成物を提供することである。 An object of the present invention is to provide a pest control composition containing thiabendazole, which reduces color change due to light or heat, is difficult to decompose even when exposed to high heat, and suppresses water loss.
　本発明者らは、上記目的を達成するために検討を重ねた結果、チアベンダゾール、テレフタル酸及び亜鉛を含有する配位高分子を用いることにより、高熱をかけても分解しにくいチアベンダゾールを含有する有害生物防除用組成物を提供することができることを見出し、本発明を完成するに至った。 As a result of repeated studies to achieve the above object, the present inventors have used a coordination polymer containing thiabendazole, terephthalic acid and zinc, which is harmful to contain thiabendazole which is difficult to decompose even under high heat. It has been found that a composition for biological control can be provided, and the present invention has been completed.
　すなわち、本発明は、以下の態様を包含する。
（１）チアベンダゾール（ＴＢＺ）、テレフタル酸（ＢＤＣ）及び亜鉛（Ｚｎ）を含有する配位高分子。
（２）式（Ｉ）
　　　[Ｚｎa（ＴＢＺ）b（ＢＤＣ）cＲd]n　　　（Ｉ）
（式中、Ｒは亜鉛イオンの対アニオンを示す。ａ，ｂ及びｃは１以上の整数、ｄは０以上の整数を示す。ｎはＺｎa（ＴＢＺ）b（ＢＤＣ）cＲdで表される構成単位の集合数であり、特に限定されない）
で表される化合物又はその溶媒付加物である、（１）に記載の配位高分子。
（３）[Ｚｎ(ＴＢＺ)(ＢＤＣ)]ｎまたは [Ｚｎ４(ＴＢＺ)2(ＢＤＣ)3]ｎ（これらの式中、ｎはＺｎ(ＴＢＺ)(ＢＤＣ)またはＺｎ４(ＴＢＺ)2(ＢＤＣ)3で表される構成単位の集合数であり、特に限定されない）で表される、（１）または（２）に記載の配位高分子。
（４）（１）～（３）のいずれかに記載の配位高分子を含む、有害生物防除組成物。
（５）抗微生物性を有する成分、殺虫剤、除草剤、植物成長調節剤のうちのいずれか１種をさらに含むものである、（４）に記載の有害生物防除組成物。
（６）工業製品の微生物汚染防除剤用である、（４）または（５）に記載の有害生物防除組成物。
（７）有害生物防除組成物が、樹脂組成物である、（６）に記載の有害生物防除組成物。
（８）有害生物防除組成物が、繊維または糸である、（６）に記載の有害生物防除組成物。 That is, the present invention includes the following aspects.
(1) Coordination polymer containing thiabendazole (TBZ), terephthalic acid (BDC) and zinc (Zn).
(2) Equation (I)
[Zn a (TBZ) b (BDC) c R d ] n (I)
(In the formula, R indicates the counter anion of zinc ion. A, b and c indicate an integer of 1 or more, d indicates an integer of 0 or more. N is represented by Zn a (TBZ) b (BDC) c R d . It is the number of sets of constituent units to be formed, and is not particularly limited.)
The coordination polymer according to (1), which is a compound represented by (1) or a solvent adduct thereof.
(3) [Zn (TBZ) (BDC)] n or [Zn 4 (TBZ) 2 (BDC) 3 ] n (in these equations, n is Zn (TBZ) (BDC) or Zn 4 (TBZ) 2 ( BDC) The coordination polymer according to (1) or (2), which is the number of sets of structural units represented by 3 and is not particularly limited).
(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), further comprising 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.
　本発明に係るチアベンダゾール含有配位高分子は、光や熱による色調変化が起こりにくく、高熱をかけても分解しにくく、水への溶脱も起こりにくいため、屋外等光が当たる場面での使用や高熱をかける分野、そして水に触れる機会の多い場面等に用いることに、特に有用である。 The thiobendazole-containing coordination polymer according to the present invention is unlikely to change in color due to light or heat, is not easily decomposed even when exposed to high heat, and is not easily leached into water. It is especially useful in fields where high heat is applied and in situations where there are many opportunities to come into contact with water.
実施例１で得た結晶の粉末Ｘ線回折（XRD）パターンを示す図である。It is a figure which shows the powder X-ray diffraction (XRD) pattern of the crystal obtained in Example 1. FIG. 実施例１で得た結晶について、Ｘ線構造解析に基づいて作成した分子モデルの部分構造を示す図である。It is a figure which shows the partial structure of the molecular model prepared based on the X-ray structure analysis about the crystal obtained in Example 1. FIG. 実施例２で得た結晶について、Ｘ線構造解析に基づいて作成した分子モデルの部分構造を示す図である。It is a figure which shows the partial structure of the molecular model prepared based on the X-ray structure analysis about the crystal obtained in Example 2. FIG. 実施例２で得た結晶及び溶媒除去後の結晶の粉末Ｘ線回折（XRD）パターンを示す図である。It is a figure which shows the powder X-ray-diffraction (XRD) pattern of the crystal obtained in Example 2 and the crystal after solvent removal. 実施例１、２で得た結晶及び比較例（TBZ）のTG－DSC（熱分析装置）による測定結果を示す図である。It is a figure which shows the measurement result by the TG-DSC (thermal analyzer) of the crystal obtained in Examples 1 and 2 and the comparative example (TBZ). 実施例１で得た結晶および比較例（TBZ）のポリカーボネート樹脂への練り込み後の耐候試験の結果の撮影図である。It is a photograph figure of the result of the weather resistance test after kneading the crystal obtained in Example 1 and the comparative example (TBZ) into a polycarbonate resin. 実施例１で得た結晶について、赤外分光光度計（FT-IR）による測定結果を示す図であり、一部を拡大して表わしている。It is a figure which shows the measurement result by the infrared spectrophotometer (FT-IR) about the crystal obtained in Example 1, and is shown by enlarging a part. 実施例１で得た結晶について、13C-CPMAS-NMR測定結果を示す図である。（a）は全体、（b）は拡大したスペクトラムであり、（上）は実施例１により得られたZn（TBZ）(BDC)、（中）は原料のBDC、（下）は原料のTBZを示す。It is a figure which shows the 13C-CPMAS-NMR measurement result about the crystal obtained in Example 1. FIG. (A) is the whole, (b) is the expanded spectrum, (top) is the Zn (TBZ) (BDC) obtained in Example 1, (middle) is the raw material BDC, and (bottom) is the raw material TBZ. Is shown.
　本発明の有害生物防除用組成物は、チアベンダゾール、テレフタル酸及び亜鉛を含有する配位高分子を含有する。 The pest control composition of the present invention contains a coordination polymer containing thiabendazole, terephthalic acid and zinc.
（１）チアベンダゾール含有配位高分子
　チアベンダゾール、テレフタル酸及び亜鉛を含有する配位高分子（以下、「チアベンダゾール含有配位高分子」という）は、亜鉛種により、異なる高分子構造を有することがあるが、いずれも有害生物防除用組成物として優れている。
　配位高分子とは、多座配位子と金属イオンからなる連続構造を持つ錯体のことである。例えば二座配位子Lと二配位の金属イオンMからは(-M-L-M-L-)構造が連なった配位高分子が生成し得る。配位高分子においては金属イオンは主鎖の中に位置している。
　本発明の場合は、亜鉛塩の種類により、異なる次元構造の配位高分子が得られるが、配位高分子の構造には特に限定はなく、いずれの構造であっても、光や熱による色調変化が軽減され、高熱をかけても分解しにくく、そして水溶脱が抑えられたチアベンダゾールを含有する有害生物防除用組成物を得ることができる。 (1) Coordination polymer containing thiabendazole A coordination polymer containing thiabendazole, terephthalic acid and zinc (hereinafter referred to as "coordination polymer containing thiabendazole") may have a different polymer structure depending on the zinc species. However, all of them are excellent as compositions for controlling harmful organisms.
Coordination polymer is a complex having a continuous structure consisting of a polydentate ligand and a metal ion. For example, a coordination polymer having a continuous (-MLML-) structure can be produced from a bidentate ligand L and a bidentate metal ion M. In the coordination polymer, the metal ion is located in the main chain.
In the case of the present invention, a coordination polymer having a different dimensional structure can be obtained depending on the type of zinc salt, but the structure of the coordination polymer is not particularly limited, and any structure may be affected by light or heat. It is possible to obtain a pest control composition containing thiabendazole, which has reduced color change, is less likely to be decomposed even when subjected to high heat, and has suppressed water loss.
　本発明の配位高分子は、以下の式（I）
　[Ｚｎa（ＴＢＺ）b（ＢＤＣ）cＲd]n　　　（I）
で表され、Ｚｎa（ＴＢＺ）b（ＢＤＣ）cＲdで表される各構成単位は、配位結合で繋がっている。溶媒が配位高分子中に取り込まれた溶媒付加物でもよい。
　式（I）中、ＴＢＺはチアベンダゾールを示し、ＢＤＣはテレフタル酸を示し、Ｒは亜鉛イオンの対アニオンを示す。対アニオンは、亜鉛化合物のアニオン部分であり、Ｆ，Ｃｌ，ＢｒまたはＩのハロゲノアニオン；ＮＯ３、ＳＯ４など無機アニオン；ＨＣＯＯ、ＣＨ３ＣＯＯ、ａｃａｃなどの有機アニオンが例示される。a、b及びcは、それぞれ独立して、１以上の整数、具体的には、１～５０、１～１０、１～５等の範囲のいずれかの整数を示し、ｄは０以上の整数、具体的には、０～５０、０～１０、０～５等の範囲のいずれかの整数を示す。ｎは、Ｚｎa（ＴＢＺ）b（ＢＤＣ）cＲdで表される構成単位の集合数であり、本発明の効果を奏することができる限り、特に限定されない。 The coordination polymer of the present invention has the following formula (I).
[Zn a (TBZ) b (BDC) c R d ] n (I)
Each structural unit represented by Zn a (TBZ) b (BDC) c R d is connected by a coordinate bond. It may be a solvent adduct in which the solvent is incorporated into the coordination polymer.
In formula (I), TBZ represents tiabendazole, BDC represents terephthalic acid, and R represents the counter anion of zinc ion. The counter anion is an anion moiety of a zinc compound, and examples thereof include halogeno 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 indicate an integer of 1 or more, specifically, an integer in the range of 1 to 50, 1 to 10, 1 to 5, etc., and d is an integer of 0 or more. Specifically, it indicates an integer in the range of 0 to 50, 0 to 10, 0 to 5, and the like. n is the number of sets 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 achieved.
　具体的には、実施例に示すように、構成単位がZn(TBZ)(BDC)、 Zn４(TBZ)2(BDC)3・6DMFなどの配位高分子が挙げられる。ここで、DMFは溶媒であるN,N-ジメチルホルムアミドを示す。
　たとえば、図２の分子モデルにより示される、構成単位がZn(TBZ)(BDC)である配位高分子の場合は、各構成単位においては、１分子のTBZ中の２つのN原子と２分子のBDC中の片方のCOOH基の2つのO原子が配位する１つのZnイオン（Zn1：配位数６）を有し、各構成単位は、BDC中の片方のCOOH基の2つのO原子が他の構成単位のZnイオン（Zn1）に配位結合することにより、直鎖状に繋がっている。
　また、図３の分子モデルにより示される、構成単位がZn４(TBZ)2(BDC)3・6DMFである配位高分子の場合は、各構成単位中の4個の亜鉛イオンは、１分子のTBZ中の１つのN原子と３分子のBDC中の片方のCOOH基の中の１つのO原子が配位する２つの亜鉛イオン（Zn１：配位数４）と、１分子のTBZ中の残りの２つのN原子と、３分子のBDC中の片方のCOOH基の１つのO原子が配位する２つの亜鉛イオン（Zn２：配位数５）を有し、各構成単位は、TBZ中のN原子とBDC中のO原子が他の構成単位の亜鉛イオン（Zn1とZn2）に配位結合することにより、ネットワーク状に繋がり、その結果、一次元チャネル空孔を形成している。そして、各構成単位中には、溶媒であるDMFが６つ取り込まれている。 Specifically, as shown in Examples, coordination polymers having constituent units such as Zn (TBZ) (BDC) and Zn 4 (TBZ) 2 (BDC) 3.6DMF can be mentioned. Here, DMF indicates the solvent N, N-dimethylformamide.
For example, in the case of a coordinated polymer whose structural unit is Zn (TBZ) (BDC) as shown by the molecular model in FIG. 2, in each structural unit, two N atoms and two molecules in one TBZ are used. It has one Zn ion (Zn1: coordination number 6) coordinated by two O atoms of one COOH group in the BDC, and each constituent unit has two O atoms of one COOH group in the BDC. Is linearly connected by a coordinate bond to the Zn ion (Zn1) of another constituent unit.
Further, in the case of a coordination polymer whose constituent unit is Zn 4 (TBZ) 2 (BDC) 3.6 DMF, which is shown by the molecular model in FIG. 3, four zinc ions in each constituent unit are one molecule. Two zinc ions (Zn1: coordination number 4) coordinated by one N atom in TBZ and one O atom in one COOH group in three molecules of BDC, and one molecule of TBZ. It has two zinc ions (Zn2: coordination number 5) coordinated by the remaining two N atoms and one O atom of one COOH group in three molecules of BDC, and each constituent unit is in TBZ. The N atom and the O atom in the BDC are coordinated and bonded to the zinc ions (Zn1 and Zn2) of other constituent units, and are connected in a network, resulting in the formation of one-dimensional channel vacancies. Six DMFs, which are solvents, are incorporated into each structural unit.
（チアベンダゾール：TBZ）
　チアベンダゾールは、次式で表される化合物であり、殺菌剤等として周知の化合物である。
Figure JPOXMLDOC01-appb-C000001
 (Tiabendazole: TBZ)
Thiabendazole is a compound represented by the following formula and is a well-known compound as a bactericidal agent or the like.
Figure JPOXMLDOC01-appb-C000001
（テレフタル酸：BDC）
　テレフタル酸は、次式で表される化合物である。
Figure JPOXMLDOC01-appb-C000002
 (Terephthalic acid: BDC)
Terephthalic acid is a compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000002
（亜鉛塩）
　亜鉛塩とは、２価の無機又は有機の亜鉛塩である。
　無機塩としては、塩酸、硫酸、硝酸等の無機酸の塩；塩化物、臭化物、ヨウ化物等のハロゲン化物を挙げることができる。
　有機塩としては、蟻酸、酢酸、乳酸、シュウ酸、クエン酸、コハク酸、リンゴ酸、安息香酸等の有機酸の塩等を挙げることができる。
　これらのうち、硝酸塩、酢酸塩、硫酸塩、塩化塩、臭化塩、ヨウ化塩、乳酸塩が好ましい。
　これらの亜鉛塩を単独で、又は、２種以上を併用しても構わない。 (Zinc salt)
The zinc salt is a divalent inorganic or organic zinc salt.
Examples of the inorganic salt 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 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.
Of these, nitrates, acetates, sulfates, chlorides, bromates, iodides, and lactates are preferred.
These zinc salts may be used alone or in combination of two or more.
（溶媒）
　合成に用いる溶媒としては、特に限定されないが、有機溶媒、水またはそれらの混合溶媒を使用することができる。溶媒は、１種単独でも、２種以上の混合溶媒でも使用することができる。
　有機溶媒として、特に限定はないが、具体的には、メタノール、エタノール、プロパノールなどのアルコール化合物；ジエチルエーテル、１，２－ジメトキシエタン、テトラヒドロフラン等のエーテル化合物；ベンゼン、トルエン等の芳香族炭化水素；塩化メチレン、クロロホルム等のハロゲン化炭化水素；アセトン、酢酸エチル、アセトニトリル、Ｎ，Ｎ－ジメチルホルムアミド（DMF）、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等が挙げられる。これらの中でも、Ｎ，Ｎ－ジメチルホルムアミドを用いることが好ましい。
　これらの溶媒は、有害生物防除の目的を阻害しない範囲で、配位高分子内に残存していてもよい。 (solvent)
The solvent used for the synthesis is not particularly limited, but an organic solvent, water or a mixed solvent thereof can be used. As the solvent, one kind alone or two or more kinds of mixed solvents can be used.
The organic solvent is not particularly limited, but specifically, 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. Hydrocarbons such as methylene chloride and chloroform; acetone, ethyl acetate, acetonitrile, N, N-dimethylformamide (DMF), N, N-diethylformamide, N, N-dimethylacetamide and the like. Among these, it is preferable to use N, N-dimethylformamide.
These solvents may remain in the coordination polymer as long as they do not interfere with the purpose of controlling pests.
（２）チアベンダゾール含有配位高分子の調製
　溶媒中で、チアベンダゾール、テレフタル酸及び亜鉛塩を混合することにより、チアベンダゾール含有配位高分子が得られる。
　混合時の条件は以下のとおりである。 (2) Preparation of Tiabendazole-Containing Coordination Polymer By mixing thiabendazole, terephthalic acid and a zinc salt in a solvent, a thiabendazole-containing coordination polymer can be obtained.
The conditions at the time of mixing are as follows.
　亜鉛塩とテレフタル酸の混合比率は、亜鉛塩：テレフタル酸＝１：５～５：１のモル比の範囲が好ましく、１：１～４：１の範囲がより好ましい。
　亜鉛塩とチアベンダゾールの混合比率は、亜鉛塩：チアベンダゾール＝１：５～５：１のモル比の範囲が好ましく、１：２～２：１の範囲がより好ましい。 The mixing ratio of the zinc salt and the terephthalic acid is preferably in the 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 and thiabendazole is preferably in the range of zinc salt: thiabendazole = 1: 5 to 5: 1, and more preferably in the range of 1: 2 to 2: 1.
　溶媒中で反応を行う際、溶媒における亜鉛塩のモル濃度は、０．００５～５mol／Lが好ましく、０．０１～２mol／Lがより好ましい。テレフタル酸のモル濃度は、０．００１～５mol／Lが好ましく、０．００５～２mol／Lがより好ましい。チアベンダゾールのモル濃度は、０．００１～５mol／Lが好ましく、０．００５～２mol／Lがより好ましい。 When the reaction is carried out in a solvent, the molar concentration of the zinc salt in the solvent is preferably 0.005 to 5 mol / L, more preferably 0.01 to 2 mol / L. The molar concentration of terephthalic acid is preferably 0.001 to 5 mol / L, more preferably 0.005 to 2 mol / L. The molar concentration of thiabendazole is preferably 0.001 to 5 mol / L, more preferably 0.005 to 2 mol / L.
　チアベンダゾール含有配位高分子は、亜鉛塩、テレフタル酸およびチアベンダゾールを混合させるだけで得られることもあるが、オートクレーブなどの耐圧容器に入れ、高温・加圧下で反応させてもよい。反応液の加熱温度は、上記所定の特性を示す配位高分子が得られれば、特に制限されないが、室温～２００℃の範囲が好ましい。加熱する場合には、１００～１５０℃であることが好ましい。 The thiabendazole-containing coordination polymer may be obtained only by mixing zinc salt, terephthalic acid and thiabendazole, but 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 exhibiting the above-mentioned predetermined characteristics can be obtained, but is preferably in the range of room temperature to 200 ° C. When heating, it is preferably 100 to 150 ° C.
　本製造方法の反応時間は上記所定の特性を示す配位高分子が得られれば、特に制限されないが、生成物の収率がより優れる点で、１時間以上が好ましく、２４時間以上がより好ましい。
　室温の場合、２４時間以上、加熱工程における加熱時間は６時間以上であることが好ましい。 The reaction time of this production method is not particularly limited as long as a coordination polymer exhibiting the above-mentioned predetermined characteristics can be obtained, but 1 hour or more is preferable, and 24 hours or more is more preferable in terms of better yield of the product. ..
In the case of room temperature, it is preferable that the heating time is 24 hours or more, and the heating time in the heating step is 6 hours or more.
　本製造方法の手順は、上記所定の特性を示す配位高分子が得られれば、特に制限されないが、例えば、溶媒の存在下、チアベンダゾール、テレフタル酸及び亜鉛塩を混合して加熱する方法が好ましく挙げられる。本製造方法においては、反応基質の混合方法は特に制限されず、公知の方法が採用できる。また、各成分を加える順番も特に限定されず、反応容器に上記成分を同時に添加しても、それぞれ順番に添加してもよい。 The procedure of this production method is not particularly limited as long as a coordination polymer exhibiting the above-mentioned predetermined characteristics is obtained, but for example, a method of mixing and heating thiabendazole, terephthalic acid and a zinc salt in the presence of a solvent is preferable. Can be mentioned. In this production method, the mixing method of the reaction substrate is not particularly limited, and a known method can be adopted. Further, the order in which each component is added is not particularly limited, and the above components may be added to the reaction vessel at the same time or may be added in order.
　上記反応系は、反応終了後、濾過または遠心分離のような分離方法により生成物と溶媒とを容易に分離することができる。
　なお、上記工程で調製された生成物は、濾過、濃縮、蒸留、抽出、晶析、再結晶、カラムクロマトグラフィー等の分離手段や、これらを組み合わせた分離手段により分離精製できる。好ましくは、濾過した後、原料のテレフタル酸、亜鉛塩が溶解する溶媒で、良く洗浄し、100℃～150℃で真空乾燥するのが望ましい。本溶媒としては、例えば前記合成に用いる溶媒と同じものを用いることができる。 In the above reaction system, after the reaction is completed, the product and the solvent can be easily separated by a separation method such as filtration or centrifugation.
The product prepared in the above step can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a separation means combining these. It is preferable that after filtering, the material is thoroughly washed with a solvent in which the raw materials terephthalic acid and zinc salt are dissolved, and vacuum dried at 100 ° C to 150 ° C. As the present solvent, for example, the same solvent as that used for the synthesis can be used.
　生成物の構造や組成、性能の確認は、一般的な手法を用いて行うことができる。例えば、Ｘ線回折測定（結晶構造の確認）、13C-CPMAS-NMR測定（生成物の組成分析）、熱分析（耐熱性の測定）等を用いることが可能である。
　Ｘ線回折測定や13C-CPMAS-NMRは粉体のまま、室温で測定し、熱分析は、粉体を室温から1000℃まで空気中加熱する事で測定する。 The structure, composition, and performance of the product can be confirmed by using a general method. 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 and 13C-CPMAS-NMR are measured at room temperature as they are, and thermal analysis is measured by heating the powder in air from room temperature to 1000 ° C.
（３）任意成分
　本発明の有害生物防除用組成物は、上記成分だけでもよいが、以下の成分を含んでもよい。 (3) Optional components The pest control composition of the present invention may contain only the above components, but may also contain the following components.
（Ａ）樹脂
　本発明有害生物防除用組成物に含有される樹脂としては、有害生物防除用組成物の用途、求められる性能等に応じて、種々の樹脂を用いることができる。樹脂としては、熱可塑性樹脂や熱又は光硬化性樹脂が挙げられる。これらは１種を単独で用いてもよく、また２種以上を併用してもよい。 (A) Resin As the resin contained in the pest control composition of the present invention, various resins can be used depending on the use of the pest control composition, the required performance and the like. Examples of the resin include thermoplastic resins and heat or photocurable resins. These may be used alone or in combination of two or more.
ａ）熱可塑性樹脂
　本発明で用いる熱可塑性樹脂としては、特に制限されないが、具体的にはスチレン系樹脂、アクリル樹脂、酢酸ビニル樹脂、アクリロニトリル共重合体、ポリフェニレンオキサイド樹脂（PPO）、ポリスルホン樹脂（PSF、PSU）、ポリエーテルスルホン（PES）、ポリアリレート（PAR）、ポリエーテルイミド（PEI）、ポリアミドイミド（ＰＡＩ）、ポリイミド（ＰＩ）、ポリメタクリル酸メチル、アクリロニトリル－スチレン共重合体（ＡＳ樹脂）、アクリロニトリル－スチレン－Ｎ－置換マレイミド三元共重合体、アクリロニトリル－ブタジエン－スチレン共重合(ABS樹脂)、スチレン－無水マレイン酸共重合体、スチレン－無水マレイン酸－Ｎ－置換マレイミド三元共重合体、ポリカーボネート樹脂（ＰＣ）、ポリブチレンテレフタレート樹脂（ＰＢＴ）、ＬＬＤＰＥ（リニア低密度ポリエチレン）、LDPE（低密度ポリエチレン）、ＨＤＰＥ（高密度ポリエチレン）、ポリエチレンテレフタレート樹脂（ＰＥＴ）、ポリ塩化ビニル（ＰＶＣ）、ポリエチレン、ポリプロピレン、人工熱可塑性ポリオレフィン（ＴＰＯ）、スチレン－ブタジエン－スチレン（ＳＢＳ）、スチレン－ ブタジエンゴム（ＳＢＲ）、水素添加ＳＢＳ 、スチレン－イソプレン－スチレン（ＳＩＳ）、各種オレフィン系エラストマー、各種ポリエステル系エラストマー、ポリスチレン(ＰＳ)、メタクリル酸メチル－スチレン共重合体（ＭＳ樹脂）、アクリロニトリル－スチレン－メタクリル酸メチル共重合体、ポリアセタール樹脂（ＰＯＭ）、変性ポリフェニレンエーテル樹脂（変性ＰＰＥ）、エチレン－酢酸ビニル共重合体(ＥＶＡ)、ポリフェニレンスルフィド樹脂（ＰＰＳ）、ポリエーテルスルホン樹脂（ＰＥＳ、ＰＥＳＵ）、ポリフェニルスルホン（ＰＰＳＵ）、ポリエーテルケトン（PEK)、ポリエーテルエーテルケトン樹脂（ＰＥＥＫ）、ポリエーテル、ポリアクリレート、液晶ポリエステル樹脂、液晶ポリマー（LCP）、ポリアミド樹脂（ナイロン）、フッ素樹脂、ポリビニルピロリドン(PVP)等挙げられる。 a) Thermoplastic resin The thermoplastic resin used in the present invention is not particularly limited, but specifically, a styrene resin, an acrylic resin, a vinyl acetate resin, an acrylonitrile copolymer, a polyphenylene oxide resin (PPO), and a polysulfone resin (. PSF, PSU), polyether sulfone (PES), polyarylate (PAR), polyetherimide (PEI), polyamideimide (PAI), polyimide (PI), polymethylmethacrylate, acrylonitrile-styrene copolymer (AS resin) ), Acrylonitrile-styrene-N-substituted maleimide ternary copolymer, acrylonitrile-butadiene-styrene copolymer (ABS resin), styrene-maleic anhydride copolymer, styrene-maleic anhydride-N-substituted maleimide ternary copolymer Polymer, 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 (PET) 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 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 sulfone resin (PES, PESU), polyphenyl sulfone (PPSU), polyether ketone (PEK), polyether ether ketone resin (PEEK), Examples thereof include polyether, polyacrylate, liquid crystal polyester resin, liquid crystal polymer (LCP), polyamide resin (nylon), fluororesin, polyvinylpyrrolidone (PVP) and the like.
ｂ）熱又は光硬化性樹脂
　本発明で用いる熱又は光硬化性樹脂としては、特に限定されないが、ビニル基、（メタ）アクリロイル基、エポキシ基、オキセタニル基を有するモノマー、プレポリマー、オリゴマー、ポリマーなどを用いることができる。なかでも多官能樹脂を用いることが好ましい。なお、本発明において、「（メタ）アクリロイル基」は、「アクリロイル基」及び／又は「メタクリロイル基」を意味する。 b) Thermal or photocurable resin The thermal or photocurable resin used in the present invention is not particularly limited, but is a monomer having a vinyl group, a (meth) acryloyl group, an epoxy group, and an oxetanyl group, a prepolymer, an oligomer, and a polymer. Etc. can be used. Above all, it is preferable to use a polyfunctional resin. In the present invention, "(meth) acryloyl group" means "acryloyl group" and / or "methacryloyl group".
　上記熱又は光硬化性樹脂として、具体的には、多官能基もしくは単官能基の（メタ）アクリレートモノマー又はアクリレートオリゴマーなどを用いることができる。なかでも重合可能な不飽和基を２つ以上有する多官能アクリレ－トなどを含んでいることが好ましい。 Specifically, as the heat or photocurable resin, a polyfunctional group or a monofunctional (meth) acrylate monomer or an acrylate oligomer can be used. Among them, it is preferable to contain a polyfunctional acrylic having two or more polymerizable unsaturated groups.
　上記単官能基のアクリレートモノマーは、分子中に（メタ）アクリレート基を１つ有するモノマーであり、例えばトリシクロデカンアクリレート、イソボルニルアクリレート、テトラヒドロフルフリルアクリレート、フェノキシエチルアクリレートなどが挙げられる。なお、本発明において、「（メタ）アクリレート基」は、「アクリレート基」及び／又は「メタクリレート基」を意味する。 The 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".
　また、上記多官能基のアクリレートモノマーは分子中に（メタ）アクリレート基を２つ以上、好ましくは２から６個を有するモノマーであり、例えばトリシクロデカンジメチロールジアクリレート、ネオペンチルグリコールジアクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート、ジオキサングリコールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジトリメチロールプロパンテトラアクリレート、ビスフェノールＡ型ポリエトキシレートジアクリレート、ジペンタエリスリトールペンタアクリレート及びジペンタエリスリトールヘキサアクリレートなどが挙げられる。 Further, the acrylate monomer of the polyfunctional group is a monomer having two or more (meth) acrylate groups in the molecule, preferably 2 to 6, for example, trimethylolpropane diacrylate, neopentyl glycol diacrylate, and the like. Neopentyl glycol diacrylate, dioxan glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, bisphenol A type polyethoxylate diacrylate, dipentaerythritol pentaacrylate And dipentaerythritol hexaacrylate and the like.
　また、アクリレートオリゴマーとしては、例えばエポキシアクリレートオリゴマー、ポリエステルポリアクリレートオリゴマー、ウレタンアクリレートオリゴマーなどが挙げられる。 Further, examples of the acrylate oligomer include epoxy acrylate oligomer, polyester polyacrylate oligomer, urethane acrylate oligomer and the like.
　これらの多官能基もしくは単官能基の（メタ）アクリレートモノマー又はオリゴマーは、１種又は２種以上を組み合わせて使用することができる。 These polyfunctional or monofunctional (meth) acrylate monomers or oligomers can be used alone or in combination of two or more.
　具体的には、例えば、ケイ素樹脂、シリコーン樹脂、アクリルシリコーン樹脂、エポキシ樹脂、ポリウレタン、フェノール樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂、ケイ素樹脂及びジアリルフタレート樹脂等が挙げられる。 Specific examples thereof include silicon resin, silicone resin, acrylic silicone resin, epoxy resin, polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, silicon resin and diallyl phthalate resin.
（Ｂ）溶媒
　本発明の有害生物防除用組成物は、チアベンダゾール、テレフタル酸及び亜鉛からなる配位高分子、あるいは、配位高分子と樹脂等との混合物を分散又は溶解させることができる溶媒を含んでもよい。溶媒としては、特に限定されないが、水；蟻酸、酢酸、乳酸、シュウ酸、クエン酸、安息香酸等の有機酸類；メタノール、エタノール、イソプロピルアルコール、イソブチルアルコール、ｎ－ブタノール等のアルコール類；エタノールアミン、ジメチルアミン、ピリジン等のアミン類；ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等のアミド類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、アセチルアセトン等のケトン類；ジエチルエーテル、ジメチルエーテル、テトラヒドロフラン等のエーテル類；エチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のエーテル基含有アルコール類；酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル等のエステル類；ヘキサン、ベンゼン、キシレン、トルエン等の炭化水素類；ジクロロメタン、四塩化炭素、クロロホルム、チリクロロエチレン等のハロゲン化炭化水素類；アセトニトリル；鉱油、合成炭化水素油、合成エステル油、天然油脂、天然油脂誘導体、エーテル油、シリコン油、フッ素油等が挙げられる。これらの溶媒を単独で、又は、２種以上を併用しても構わない。 (B) Solvent The composition for controlling pests of the present invention comprises a coordination polymer composed of thiabendazole, terephthalic acid and zinc, or a solvent capable of dispersing or dissolving a mixture of the coordination polymer and a resin or the like. It may be included. The solvent is not particularly limited, but is water; organic acids such as formic acid, acetic acid, lactic acid, oxalic acid, citric acid, and benzoic acid; alcohols such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, and n-butanol; ethanolamine. , Dimethylamine, amines such as pyridine; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; ketones such as acetone, methylethylketone, methylisobutylketone, cyclohexanone, acetylacetone; ethers such as diethyl ether, dimethylether, tetrahydrofuran Classes; 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; dichloromethane, Halogenized hydrocarbons such as carbon tetrachloride, chloroform and chilichloroethylene; acetonitrile; mineral oils, synthetic hydrocarbon oils, synthetic ester oils, natural fats and oils, natural fat and oil derivatives, ether oils, silicon oils, fluorine oils and the like. These solvents may be used alone or in combination of two or more.
（Ｃ）その他
　本発明の有害生物防除用組成物には、本発明の効果を損なわない範囲で、目的に応じて、さらに種々の成分を加えることができる。このような成分としては、難燃剤、熱安定剤、酸化防止剤、滑剤、帯電防止剤、紫外線防止剤、着色剤、離型剤、遮熱剤、分散剤、界面活性剤、ｐＨ調整剤、消泡剤、防錆剤、粘度調整剤、金属封鎖剤、摩擦調整剤、他の抗菌成分、殺菌成分、抗ウイルス成分、防黴成分、防腐成分等の抗微生物性を有する成分、殺虫剤、除草剤、植物成長調節剤などが挙げられる。これらは二種以上を併用して用いることができる。 (C) Others Various components can be further added to the pest control composition of the present invention as long as the effects of the present invention are not impaired. Such components include flame retardants, heat stabilizers, antioxidants, lubricants, antibacterial agents, UV inhibitors, colorants, mold release agents, heat shields, dispersants, surfactants, pH regulators, etc. Antimicrobial components such as defoaming agents, rust preventives, viscosity regulators, metal sequestering agents, friction modifiers, other antibacterial components, bactericidal components, antiviral components, antifungal components, antiseptic components, insecticides, Examples include herbicides and plant growth regulators. These can be used in combination of two or more.
（難燃剤）
　難燃剤としては、特に限定されないが、例えば、塩素系及び臭素系等のハロゲン系難燃剤；リン系難燃剤等の有機系難燃剤；含窒素難燃剤、アンチモン系難燃剤、金属水酸化物系難燃剤、ホウ素系難燃剤（ホウ酸難燃剤）、赤リン系難燃剤等の無機系難燃剤を使用することができる。これらは二種以上を併用して用いることができる。 (Flame retardants)
The flame retardant is not particularly limited, but for example, a halogen-based flame retardant such as chlorine-based or bromine-based; an organic-based flame retardant such as a phosphorus-based flame retardant; a nitrogen-containing flame retardant, an antimony-based flame retardant, or a metal hydroxide-based flame retardant. Inorganic flame retardants such as flame retardants, boron-based flame retardants (boric acid flame retardants), and red phosphorus flame retardants can be used. These can be used in combination of two or more.
（熱安定剤）
　熱安定剤としては、特に限定されないが、例えば、亜リン酸エステル、リン酸エステル等のリン系熱安定剤を挙げることができる。
　亜リン酸エステルとしては、例えば、トリフェニルホスファイト、トリス（ノニルフェニル）ホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、トリノニルホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジステアリルペンタエリスリトールジホスファイト、トリシクロヘキシルホスファイト、モノブチルジフエニルホスファイト、モノオクチルジフエニルホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールホスファイト、ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）ペンタエリスリトールホスファイト、２，２－メチレンビス［（４，６－ジ－ｔｅｒｔ－ブチルフェニル）オクチルホスファイト］等の亜リン酸のトリエステル、ジエステル、モノエステル等が挙げられる。
　リン酸エステルとしては、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリス（ノニルフェニル）ホスフェート、２－エチルフェニルジフェニルホスフェート、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）－４，４－ジフエニレンホスフォナイト等が挙げられる。 (Heat stabilizer)
The heat stabilizer is not particularly limited, and examples thereof include phosphorus-based heat stabilizers such as phosphite ester and phosphoric acid ester.
Examples of the phosphorous acid ester include triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonylphosphite, tridecylphosphite, and trioctyl. Phosphite, Trioctadecylphosphite, Distearylpentaerythritol diphosphite, Tricyclohexylphosphite, Monobutyldiphenylphosphite, Monooctyldiphenylphosphite, Distearylpentaerythritol 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) ) Octylphosphite] and other phosphorous acid triesters, diesters, monoesters and the like.
Phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, and tetrakis (2,4-di-). tert-butylphenyl) -4,4-diphenylene phosphonite and the like can be mentioned.
（酸化防止剤）
　酸化防止剤としては、特に限定されないが、例えば、フェノール系酸化防止剤、リン系酸化防止剤、ホスファイト系酸化防止剤、チオ尿素系酸化防止剤等が挙げられる。 (Antioxidant)
The antioxidant is not particularly limited, and examples thereof include a phenol-based antioxidant, a phosphorus-based antioxidant, a phosphite-based antioxidant, and a thiourea-based antioxidant.
（滑剤）
　滑剤としては、特に限定されないが、例えば、高級脂肪酸、エステルワックス類、ポリエチレンワックス類、金属石鹸類等が挙げられる。 (Glidant)
The lubricant is not particularly limited, and examples thereof include higher fatty acids, ester waxes, polyethylene waxes, and metal soaps.
（帯電防止剤）
帯電防止剤としては、特に限定されないが、例えば、脂肪酸アミン、脂肪酸アルコール、脂肪酸エステル、脂肪酸アマイド、スルホン酸化合物等が挙げられる。 (Antistatic agent)
The antistatic agent is not particularly limited, and examples thereof include fatty acid amines, fatty acid alcohols, fatty acid esters, fatty acid amides, and sulfonic acid compounds.
（紫外線防止剤）
　紫外線防止剤としては、特に限定されないが、例えば、サリチル酸誘導体化合物、ベンゾフェノン化合物、ベンゾトリアゾール誘導体等のベンゾトリアゾール系化合物、シアノアクリレート化合物等が挙げられる。 (UV protection agent)
The ultraviolet inhibitor is not particularly limited, and examples thereof include benzotriazole compounds such as salicylic acid derivative compounds, benzophenone compounds, and benzotriazole derivatives, and cyanoacrylate compounds.
（着色剤）
　着色剤としては、特に限定されないが、例えば、有機顔料、無機顔料、染料、光輝剤等が挙げられる。有機顔料としては、例えば、フタロシアニン系、ベンズイミダゾロン系、アゾ系、アゾメチンアゾ系、アゾメチン系、アンスラキノン系、ぺリノン・ペリレン系、インジゴ・チオインジゴ系、ジオキサジン系、キナクリドン系、イソインドリン系、イソインドリノン系顔料等やカーボンブラック顔料等が挙げられ、無機顔料としては、例えば、体質顔料、酸化チタン系顔料、酸化鉄系顔料、スピンネル顔料等が挙げられる。更に詳細には、トルイジンレッド、トルイジンマルーン、ハンザイエロー、ベンジジンイエロー、ピラゾロンレッド等の不溶性アゾ顔料、リトールレッド、ヘリオボルドー、ピグメントスカーレット、パーマネントレッド２Ｂ等の溶性アゾ顔料、フタロシアニンブルー、フタロシアニングリーン等のフタロシアニン系、キナクリドンレッド、キナクリドンマゼンタ等のキナクリドン系、ペリレンレッド、ペリレンスカーレット等のペリレン系、イソインドリノンイエロー、イソインドリノンオレンジ等のイソインドリノン系、ピランスロンレッド、ピランスロンオレンジ等のピランスロン系、チオインジゴ系、縮合アゾ系、ベンズイミダゾロン系、キノフタロンイエロー、ニッケルアゾイエロー、ペリノンオレンジ、アンスロンオレンジ、ジアンスラキノニルレッド、ジオキサジンバイオレット等の従来公知の顔料が使用できる。染料としては、例えば、直接染料、塩基性染料、カチオン染料、酸性染料、媒染染料、酸性媒染染料、硫化染料、ナフトール染料、分散染料、反応染料等の従来公知の染料が使用できる。光輝剤としては、アルミニウムペースト、マイカ、リン片状酸化鉄などが挙げられる。 (Colorant)
The colorant is not particularly limited, and examples thereof include organic pigments, inorganic pigments, dyes, and brighteners. Examples of organic pigments include phthalocyanine-based, benzimidazolone-based, azo-based, azomethine-azo-based, azomethine-based, anthracinone-based, perinone-perylene-based, indigo-thioindigo-based, dioxazine-based, quinacridone-based, isoindrin-based, and iso. Examples thereof include indolinone pigments and carbon black pigments, and examples of the inorganic pigments include extender pigments, titanium oxide pigments, iron oxide pigments and spinnel pigments. More specifically, insoluble azo pigments such as toluidin red, toluidin maroon, hanza yellow, benzidine yellow, pyrazolon red, soluble azo pigments such as litol red, heliobordeaux, pigment scarlet, permanent red 2B, phthalocyanine blue, phthalocyanine green and the like. Phthalocyanine, quinacridone red, quinacridone magenta, etc., perylene red, perylene carlet, etc., isoindolinone yellow, isoindolinone orange, etc. Conventionally known pigments such as thioindigo-based, condensed azo-based, benzimidazolone-based, quinophthalone yellow, nickel azo yellow, perinone orange, anthlon orange, dianthraquinonyl red, and dioxazine violet can be used. As the dye, for example, conventionally known dyes such as direct dyes, basic dyes, cationic dyes, acidic dyes, medium dyes, acidic medium dyes, sulfide dyes, naphthol dyes, disperse dyes, and reactive dyes can be used. Examples of the glittering agent include aluminum paste, mica, and flaky iron oxide.
（離型剤）
　離型剤としては、特に限定されないが、例えば、脂肪族カルボン酸、脂肪族カルボン酸とアルコールとのエステル、数平均分子量２００～１５０００の脂肪族炭化水素、ポリシロキサン系シリコーンオイル等を挙げることができる。
　脂肪族カルボン酸としては、飽和又は不飽和の脂肪族１価、２価若しくは３価カルボン酸を挙げることができる。ここで脂肪族カルボン酸とは、脂環式のカルボン酸も包含する。脂肪族カルボン酸の具体例としては、パルミチン酸、ステアリン酸、カプロン酸、カプリン酸、ラウリン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、メリシン酸、テトラリアコンタン酸、モンタン酸、アジピン酸、アゼライン酸等を挙げることができる。
　脂肪族カルボン酸とアルコールとのエステルにおける脂肪族カルボン酸としては、前記脂肪族カルボン酸と同じものが使用できる。この脂肪族カルボン酸と反応しエステルを形成するアルコールとしては、飽和又は不飽和の１価アルコール、飽和又は不飽和の多価アルコール等を挙げることができる。ここで脂肪族とは、脂環式化合物も含有する。これらのアルコールの具体例としては、オクタノール、デカノール、ドデカノール、ステアリルアルコール、ベヘニルアルコール、エチレングリコール、ジエチレングリコール、グリセリン、ペンタエリスリトール、２，２－ジヒドロキシペルフルオロプロパノール、ネオペンチレングリコール、ジトリメチロールプロパン、ジペンタエリスリトール等を挙げることができる。これらの脂肪族カルボン酸とアルコールとのエステル化合物は、不純物として脂肪族カルボン酸及び／又はアルコールを含有していてもよく、複数の化合物の混合物であってもよい。 (Release agent)
The release agent is not particularly limited, and examples thereof include an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000, and a polysiloxane-based silicone oil. can.
Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, araquinic acid, bechenic acid, lignoseric acid, cellotic acid, melissic acid, tetrariacontanic acid, montanic acid and adipic acid. , Azelaic acid and the like.
As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, the same one as the above-mentioned aliphatic carboxylic acid 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, the aliphatic term also contains an alicyclic compound. 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, and dipentaerythritol. And so on. These ester compounds of the aliphatic carboxylic acid and the alcohol may contain the aliphatic carboxylic acid and / or the alcohol as impurities, or may be a mixture of a plurality of compounds.
　脂肪族カルボン酸とアルコールとのエステルの具体例としては、蜜ロウ（ミリシルパルミテートを主成分とする混合物）、ステアリン酸ステアリル、ベヘン酸ベヘニル、ベヘン酸ステアリル、グリセリンモノパルミテート、グリセリンモノステアレート、グリセリンジステアレート、グリセリントリステアレート、ペンタエリスリト－ルモノパルミテート、ペンタエリスリトールモノステアレート、ペンタエリスリトールジステアレート、ペンタエリスリトールトリステアレート、ペンタエリスリトールテトラステアレートを挙げることができる。
　数平均分子量２００～１５０００の脂肪族炭化水素としては、流動パラフィン、パラフィンワックス、マイクロワックス、ポリエチレンワックス、フィッシャートロプシュワックス又は炭素数３～１２のα－オレフィンオリゴマー等を挙げることができる。ここで脂肪族炭化水素としては、脂環式炭化水素も含まれる。また、これらの炭化水素化合物は部分酸化されていてもよい。
　ポリシロキサン系シリコーンオイルとしては、例えば、ジメチルシリコーンオイル、フェニルメチルシリコーンオイル、ジフェニルシリコーンオイル、フッ素化アルキルシリコーン等が挙げられる。これらは、単独で使用しても二種以上を混合して使用してもよい。 Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monosteer. Examples thereof include rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.
Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fishertroph wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon also includes an alicyclic hydrocarbon. Moreover, these hydrocarbon compounds may be partially oxidized.
Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. These may be used alone or in combination of two or more.
（遮熱剤）
　遮熱剤としては、赤外線（近赤外線）の遮蔽剤や吸収性色素、反射顔料（遮熱顔料）等、当業者が一般的に用いるものであれば、特に限定されない。 (Heat shield)
The heat-shielding agent is not particularly limited as long as it is generally used by those skilled in the art, such as an infrared (near-infrared) shielding agent, an absorbent dye, and a reflective pigment (heat-shielding pigment).
（分散剤）
　分散剤は、無機・有機顔料等固体粒子を媒体中に均一に分散させ、安定な分散体を調製するために使用される添加剤である。粒子分散という目的を達成できる限り特に限定されないが、例えば各種の界面活性剤等を使用することができる。 (Dispersant)
The dispersant is an additive used to uniformly disperse solid particles such as inorganic and organic pigments in a medium to prepare a stable dispersion. Although not particularly limited as long as the object of particle dispersion can be achieved, various surfactants and the like can be used, for example.
（界面活性剤）
　界面活性剤としては、ノニオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤等が挙げられる。
　ノニオン系界面活性剤としては、例えば、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレンアリールフェニルエーテル、ポリオキシアルキレンアルキルエーテル、ソルビタン脂肪酸エステル、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシアルキレン植物油などが挙げられる。
　アニオン系界面活性剤としては、例えば、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、リグニンスルホン酸塩、ナフタレンスルホン酸塩ホルムアルデヒド縮合物、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、ジアルキルスルホコハク酸塩などが挙げられる。
　カチオン系界面活性剤としては、例えば、脂肪族アミン塩、４級アンモニウム塩などが挙げられる。
　両性界面活性剤としては、例えば、アルキルベタイン型界面活性剤、アミドプロピルベタイン型界面活性剤、イミダゾリニウムベタイン型界面活性剤、スルホベタイン型界面活性剤、ホスホベタイン型界面活性剤などが挙げられる。
　これらの界面活性剤は１種単独でまたは２種以上を組み合わせて用いることができる。 (Surfactant)
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and the like.
Examples of the nonionic surfactant include polyoxyalkylene alkylphenyl ether, polyoxyalkylene arylphenyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene vegetable oil and the like.
Examples of the anionic surfactant include alkylbenzene sulfonates, alkylnaphthalene sulfonates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkyl phenyl ether sulfates. , Dialkylsulfosuccinate and the like.
Examples of the cationic surfactant include aliphatic amine salts and quaternary ammonium salts.
Examples of the amphoteric surfactant include an alkyl betaine type surfactant, an amidopropyl betaine type surfactant, an imidazolinium betaine type surfactant, a sulfobetaine type surfactant, a phosphobetaine type surfactant and the like. ..
These surfactants can be used alone or in combination of two or more.
（ｐH調整剤）
　ｐＨ調整剤としては、特に限定されないが、例えば、コハク酸や クエン酸、酒石酸、酢酸等の有機酸やそれらの塩、リン酸やポリリン酸、ホウ酸等の無機酸やそれらの塩等が挙げられる。 (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 salts thereof, and inorganic acids such as phosphoric acid, polyphosphoric acid and boric acid and salts thereof. Be done.
（消泡剤）
　消泡剤としては、特に限定されないが、例えば、鉱油系、シリコーン系、ポリエーテル系、フルオロアルキルエーテル、ポリアルキレングリコール系等の消泡剤が挙げられる。 (Defoamer)
The defoaming agent is not particularly limited, and examples thereof include mineral oil-based, silicone-based, polyether-based, fluoroalkyl ether, and polyalkylene glycol-based defoaming agents.
（防錆剤）
　防錆剤としては、特に限定されないが、例えば、金属スルホネート、アルキルベンゼンスルホネート、ジノニルナフタレンスルホネート、有機亜リン酸エステル、有機リン酸エステル、有機スルホン酸金属塩、有機リン酸金属塩、アルケニルコハク酸エステル、多価アルコールエステル、ベンゾトリアゾール系化合物等が挙げられる。 (anti-rust)
The rust preventive is not particularly limited, but for example, metal sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, organic subphosphate ester, organic phosphate ester, organic sulfonic acid metal salt, organic phosphate metal salt, alkenyl succinic acid. Examples thereof include esters, polyhydric alcohol esters, benzotriazole-based compounds and the like.
（粘度調整剤）
　粘度調整剤としては特に限定されないが、例えば、キサンタンガム、カルボキシメチルセルロース、ヒドロキシエチルセルロース、アラビアガム、ジェランガム、プルラン等が挙げられる。 (Viscosity adjuster)
The viscosity adjusting agent is not particularly limited, and examples thereof include xanthan gum, carboxymethyl cellulose, hydroxyethyl cellulose, gum arabic, gellan gum, pullulan and the like.
（金属封鎖剤）
　金属封鎖剤としては、特に限定されないが、例えば、エチレンジアミン四酢酸またはその塩、ニトリロ三酢酸またはその塩、ジエチレントリアミン五酢酸またはその塩、ヒドロキシエチルエチレンジアミン三酢酸またはその塩、トリエチレンテトラミン六酢酸またはその塩、１，３－プロパンジアミン四酢酸またはその塩、１，３－ジアミノ－２－ヒドロキシプロパン四酢酸またはその塩、１－ヒドロキシエチリデン－１，１－ジホスホン酸またはその塩、ヒドロキシエチルイミノ二酢酸またはその塩、ジヒドロキシエチルグリシンまたはその塩、グリコールエーテルジアミン四酢酸またはその塩、ジカルボキシメチルグルタミン酸またはその塩、ニトリロトリスメチレンリン酸またはその塩等が挙げられる。 (Metal sealant)
The metal sequestering agent is not particularly limited, and is, for example, ethylenediamine tetraacetic acid or a salt thereof, nitrilotriacetic acid or a salt thereof, diethylenetriaminepentacetic acid or a salt thereof, hydroxyethylethylenediaminetriacetic acid or a salt thereof, triethylenetetraminehexacetic acid or a salt thereof. Salt, 1,3-propanediaminetetraacetic acid or a salt thereof, 1,3-diamino-2-hydroxypropanetetraacetic acid or a salt thereof, 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof, hydroxyethyliminodiacetic acid Alternatively, examples thereof include dihydroxyethylglycine or a salt thereof, glycol ether diaminetetraacetic acid or a salt thereof, dicarboxymethyl glutamate or a salt thereof, nitrilotrismethylene phosphate or a salt thereof, and the like.
（摩擦調整剤）
　摩擦調整剤としては、特に限定されないが、例えば、脂肪酸、脂肪酸エステル、アルコール等が挙げられる。 (Friction modifier)
The friction modifier is not particularly limited, and examples thereof include fatty acids, fatty acid esters, and alcohols.
（他の抗菌成分、殺菌成分、抗ウイルス成分、防黴成分、防腐成分等の抗微生物性を有する成分）
　他の抗菌成分、殺菌成分、抗ウイルス成分、防黴成分、防腐成分等の抗微生物性を有する成分としては、特に制限なく用いることができる。用いる活性成分は、液状であっても固体であってもよく、有機化合物であっても無機化合物であってもよく、また、単一化合物であっても混合物であってもよい。これらは任意の比率で混合して用いることができ、1成分又は複数種類の成分を組み合わせて用いることができる。 (Other antibacterial components, bactericidal components, antiviral components, antifungal components, antiseptic components, and other antimicrobial components)
Other components having antimicrobial properties such as antibacterial components, bactericidal components, antiviral components, antifungal components, antiseptic components and the like can be used without particular limitation. The active ingredient used may be a liquid or a solid, 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 plurality of kinds of components can be used in combination.
　以下に、具体例を示す。
　抗菌成分、殺菌成分、抗ウイルス成分、防黴成分、防腐成分等としては、ベノミル、カルベンダジム、チアベンダゾール、チオファネートメチルなどのベンズイミダゾール系化合物；ジエトフェンカルブなどのフェニルカーバメート系化合物；プロシミドン、イプロジオン、ビンクロゾリンなどのジカルボキシイミド系化合物；トリフルミゾール、ヘキサコナゾール、ジニコナゾール、エポキシコナゾール、テブコナゾール、ジフェノコナゾール、シプロコナゾール、プロピコナゾール、フルシラゾール、トリアジメフォン、メトコナゾール、ミクロブタニル、イマザリル、トリホリンなどのアゾール系化合物；メタラキシルなどのアシルアラニン系化合物；フラメトピル、メプロニル、フルトラニル、トリフルザミドなどのカルボキシアミド系化合物；トルクロホスメチル、フォセチルアルミニウム、ピラゾホスなどの有機リン系化合物；ピリメサニル、メパニピリム、シプロジニルなどのアニリノピリミジン系化合物；フルジオキソニル、フェンピクロニルなどのシアノピロール系化合物；ブラストサイジンＳ、カスガマイシン、ポリオキシン、バリダマイシンなどの抗生物質；アゾキシストロビン、ピラクロストロビン、トリフロキシストロビン、クレソキシムメチル、ＳＳＦ－１２６などのメトキシアクリレート系化合物；イミノクタジン酢酸塩、イミノクタジンアルベシル酸塩、ペンフルフェン、クロロタロニル、マンゼブ、キャプタン、フォルペット、オキシン銅、塩基性塩化銅、トリシクラゾール、ピロキロン、プロベナゾール、フサライド、シモキサニル、ジメトモルフ、ＣＧＡ２４５７０４、ファモキサドン、オキソリニック酸、フルアジナム、フェリムゾン、クロベンチアゾン、イソバレジオン、チオフタルイミドオキシビスフェノキシアルシン、３－アイオド－２－プロピルブチルカーバメイト、ジデシルジメチルアンモニウムクロライド（ＤＤＡＣ）、ジデシルジメチルアンモニウムアジペート（ＤＤＡＡ）、塩化ベンザルコニウム、Ｎ，Ｎ－ジデシル－N－メチル－ポリオキシエチル－アンモニウムプロピオネ－ト（DMPAP）、Ｎ，Ｎ－ジデシル－Ｎ，Ｎ－ジメチルアンモニウム重炭酸塩、Ｎ，Ｎ－ジデシル－Ｎ，Ｎ－ジメチルアンモニウム炭酸塩などの第４級アンモニウム塩系化合物、ポリヘキサメチレンビグアニド（ＰＨＭＢ）、ポリヘキサメチレングアニジン（ＰＨＭＧ）、グルコン酸クロルへキシジンなどのビグアナイド系化合物、セチルピリジニウムクロライド、ドデシルピリジニウムクロライドなどのピリジニウム系化合物、３－ヨード－２－プロピニル－ブチルカーバメート（IPBC）などの有機ヨウ素系化合物、２，３，５，６－テトラクロロ－４－（メチルスルホニル）ピリジン（TCMSP）などのピリジン系化合物、ジンクピリチオン、ナトリウムピリチオンなどのピリチオン系化合物、２－（４－チオシアノメチルチオ）ベンゾチアゾールなどのベンゾチアゾール系化合物、メチル－２－ベンズイミダゾールカーバメート、２－（４－チアゾリル）－ベンズイミダゾールなどのイミダゾール系化合物、テトラメチルチウラムジスルフィドなどのチオカーバメート系化合物、２，４，５，６－テトラクロロイソフタロニトリルなどのニトリル系化合物、Ｎ－（フルオロジクロロメチルチオ）－フタルイミド、Ｎ－（フルオロジクロロメチルチオ）－Ｎ，Ｎ’－ジメチル－Ｎ－フェニル－スルファミドなどのハロアルキルチオ系化合物、α－ｔ－ブチル－α（ｐ－クロロフェニルエチル）－１Ｈ－１，２，４－トリアゾール－１－エタノール（慣用名テブコナゾール）などのトリアゾール系化合物、１，２－ベンズイソチアゾリン－３－オン、Ｎ－メチル－１，２－ベンズイソチアゾール－３（２H）－オン、２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン、５－クロロ－２－メチル－４－イソチアゾリン－３－オン、２－メチル－４－イソチアゾリン－３－オン、２－ｎ－オクチル－４－イソチアゾリン－３－オン、４，５－ジクロロ－２－ｎ－オクチル－４－イソチアゾリン－３－オン、２－エチル－４－イソチアゾリン－３－オン、４，５－ジクロロ－２－シクロヘキシル－４－イソチアゾリン－３－オン、５－クロロ－２－エチル－４－イソチアゾリン－３－オン、５－クロロ－２－メチル－４－イソチアゾリン－３－オン、５－クロロ－２－ｔ－オクチル－４－イソチアゾリン－３－オン、２－ｎ－ブチル－１，２ベンズイソチアゾリン－３－オン、４，５－ジクロロ－２－n－オクチル－４－イソチアゾリン－３－オンなどのイソチアゾリン系化合物、２－ブロモ－２－ニトロ－１，３－プロパンジオール、２，２－ジブロモ－２－ニトロエタノール、２，２－ジブロモ－３－ニトリロプロピオンアミドなどの臭素系化合物、パラクロロメタクレゾール、４－クロロ－３，５－キシレノール、トリアジン－１，３，５（2H，４H，６H）－トリエタノール、ストレプトマイシン、ジウロン（ＤＣＭＵ）、ダイムロン、メトベンズロン、クミルロン、ニコスルフロン、リニュロン、シブトリン、テルブトリン、シマジン、アトラジン、プロパジン、シアナジン、ジメタメトリン、プロメトリン、ブトラリン、ベンフルラリン、プロジアミン、ベンゾフェナップ、ピラフルフェン－エチル、ビフェノックス、ブロモブチド、ブロモキシニル、プロパニル、ジフルフェニカン、メフェナセット、クロメプロップ、ジクロスラム、ジチオピル、イソキサベン、レナシル、ピリブチカルブ、ピリミノバック－メチル、オキサジアゾン、オリザリン、オキサジアルギル、フルチアセット－メチル、ピリベンゾキシム、ペントキサゾン、銀ゼオライト、シリカゲル銀、リン酸ジルコニウム銀塩、ヒスチジン銀錯体、パラヒドロキシ安息香酸エステル、安息香酸ナトリウム、デヒドロ酢酸ナトリウム、ソルビン酸カリウム、メチルパラベン、メチレンビスチオシアネート、酸化第二銅、水酸化第二銅、クレオソート油、リチウム塩、ナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩などを挙げることができる。 A specific example is shown below.
Examples of the antibacterial component, bactericidal component, antiviral component, antifungal component, antiseptic component, etc. include benzimidazole compounds such as benomil, carbendazim, thiabendazole, and thiophanatemethyl; phenylcarbamate compounds such as dietofencarb; Dicarboxyimide compounds; azole compounds such as triflumizole, hexaconazole, diniconazole, epoxyconazole, tebuconazole, diphenoconazole, cyproconazole, propiconazole, flusilazole, triazimephon, methconazole, microbutanyl, imazalyl, triphorin. Acylalanine compounds such as metalaxyl; Carboxamide compounds such as flametopyl, mepronyl, flutranyl and trifluzamide; Organic phosphorus compounds such as turquophosmethyl, fosetylaluminum and pyrazophos; Anilinopyrimidine compounds such as pyrimesanyl, mepanipylim and cyprodinyl Cyanopyrrole compounds such as fludioxonyl and fenpicronyl; Antibiotics such as blastsaidin S, casgamicin, polyoxin, and varydamycin; Compounds; iminoctazine acetate, iminoctazine albesilate, penflufen, chlorotalonyl, manzeb, captan, folpet, oxine copper, basic copper chloride, tricyclazole, pyrochyron, probenazole, fusalide, simoxanyl, dimethomorph, CGA245704, famoxadon, oxolinic acid, Fluazinum, Felimzone, Clobenazone, Isovalegion, Thiophthalimideoxybisphenoxyarcin, 3-iodo-2-propylbutylcarbamate, Didecyldimethylammonium chloride (DDAC), Didecyldimethylammonium adipate (DDAA), benzalconium chloride, N, N-didecil-N-methyl-polyoxyethyl-ammonium propionate (DMPAP), N, N-didecil-N, N-dimethylammonium bicarbonate, N, N-didecil-N, N-dimethyl Tertiary ammonium salt compounds such as ammonium carbonate, polyhexamethylene biguanide (PHMB), polyhexamethyleneguanidine (PHMG), glucon Biguanide compounds such as chlorhexidine acid, pyridinium compounds such as cetylpyridinium chloride and dodecylpyridinium chloride, organic iodine compounds such as 3-iodo-2-propynyl-butylcarbamate (IPBC), 2,3,5,6 -Ppyridine compounds such as tetrachloro-4- (methylsulfonyl) pyridine (TCMSP), pyrithion compounds such as zinc pyrithione and sodium pyrithione, benzothiazole compounds such as 2- (4-thiocyanomethylthio) benzothiazole, methyl- 2-Benzimidazole carbamate, imidazole compounds such as 2- (4-thiazolyl) -benzimidazole, thiocarbamate compounds such as tetramethylthium disulfide, and nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile. Compounds, haloalkylthio compounds such as N- (fluorodichloromethylthio) -phthalimide, N- (fluorodichloromethylthio) -N, N'-dimethyl-N-phenyl-sulfamide, α-t-butyl-α (p-chlorophenyl) Ethyl) -1H-1,2,4-triazole-1-ethanol (commonly known as tebuconazole) and other triazole compounds, 1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazole- 3 (2H) -one, 2-methyl-4,5-trimethylethylene-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3 -On, 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, 4,5-dichloro-2-n-octyl-4-isothiazolin-3 Isothiazolin-based compounds such as -one, bromine-based compounds such as 2-bromo-2-nitro-1,3-propanediol, 2,2-dibromo-2-nitroethanol, and 2,2-dibromo-3-nitrilopropionamide. , Parachloromethacresol , 4-Chloro-3,5-xylenol, Triazine-1,3,5 (2H, 4H, 6H) -Triethanol, Streptomycin, Diuron (DCMU), Dimulon, Metobenzlon, Cumyllon, Nicosulfron, Linuron, Sibutrin, Telbutrin , Simazine, Atlasin, Propazine, Cyanazine, Dimetamethrin, Promethrin, Butraline, Benflularin, Prodiamine, Benzophenap, Pyrflufen-ethyl, Biphenox, Bromobutide, Bromoxinyl, Propanyl, Diflufenican, Mephenacet, Chromeprop, Dicrosslam, Dithiopyl, Isoxaben Pyributycarb, pyriminobac-methyl, oxadiazone, oryzarin, oxadiargyl, fluthiaset-methyl, pyribenzoxim, pentoxazone, silver zeolite, silica gel silver, zirconium phosphate silver salt, histidine silver complex, parahydroxybenzoic acid ester, sodium benzoate, sodium dehydroacetate , Potassium sorbate, methylparaben, methylene bisthiocyanate, cupric oxide, cupric hydroxide, cleosort oil, lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt and the like.
（殺虫剤、除草剤、植物成長調節剤など）
　本発明の有害生物防除用組成物は、殺虫剤、除草剤、植物成長調節剤等と共に組成物として用いることもできる。これらの成分としては、特に制限なく用いることができる。用いる活性成分は、液状であっても固体であってもよく、有機化合物であっても無機化合物であってもよく、また、単一化合物であっても混合物であってもよい。これらは任意の比率で混合して用いることができ、1成分又は複数種類の成分を組み合わせて用いることができる。
　以下に、具体例を示す。
　殺虫剤としては、シフルトリン、シペルメトリン、デルタメトリン、フェンプロパトリン、フェンバレレート、エスフェンバレレート、トラロメトリン、アクリナトリン、ビフェントリン、レスメトリン、テトラメトリン、テフルトリン、エトフェンプロックス、シフェノトリン、ペルメトリン、プラレトリン、ピレトリン、シラフルオフェンなどのピレスロイド系化合物；プロポキサー、イソプロカルブ、キシリルカルブ、メトルカルブ、ＸＭＣ、カルバリル、ピリミカルブ、カルボフラン、メソミル、フェノキシカルブ、アラニカルブ、メトキサジアゾンなどのカーバメート系化合物；アセフェート、フェントエート、バミドチオン、トリクロルホン、モノクロトホス、テトラクロルビンホス、ジメチルビンホス、ホサロン、クロルピリホス、クロルピリホスメチル、ピリダフェンチオン、キナルホス、メチダチオン、メタミドホス、ジメトエート、フェルモチオン、アジンホスエチル、アジンホスメチル、サリチオン、フェニトロチオンなどの有機リン系化合物；ジフルベンズロン、クロルフルアズロン、ルフェヌロン、ヘキサフルムロン、フルフェノクスロン、フルシクロクスロン、シロマジン、ジアフェンチウロン、ヘキシチアゾクス、ノヴァルロン、テフルベンズロン、トリフルムロン、４－クロロ－２－（２－クロロ－２－メチルプロピル）－５－（６－ヨード－３－ピリジルメトキシ）ピリダジン－３（２Ｈ）－オン、１－（２，６－ジフルオロベンゾイル）－３－［２－フルオロ－４－（トリフルオロメチル）フェニル］ウレア、１－（２，６－ジフルオロベンゾイル）－３－［２－フルオロ－４－（１，１，２，３，３，３－ヘキサフルオロプロポキシ）フェニル］ウレア、２－ｔｅｒｔ－ブチルイミノ－３－イソプロピル－５－フェニル－３，４，５，６－テトラヒドロ－２Ｈ－１，３，５－チアジアゾン－４－オン、１－（２，６－ジフルオロベンゾイル）－３－［２－フルオロ－４－（１，１，２，２－テトラフルオロエトキシ）フェニル］ウレアなどのウレア系化合物；イミダクロプリド、アセタミプリド、ニテンピラム、ジアクロデン、チアメトキサム、クロチアニジン、チアクロプリド、ジノテフランなどのネオニコチノイド系化合物；フィプロニル、カルタップ、ブプロフェジン、チオシクラム、ベンスルタップ、フェノキシカルブ、フェナザキン、フェンピロキシメート、ピリダベン、リプロキシフェン、ヒドラメチルノン、チオジカルブ、フェノブカルブ、クロルフェナピル、フェンプロキシメート、ピメトロジン、ピリミジフェン、テブフェノジド、テブフェンピラド、メトキシフェノジド、トリアザメート、インドキサカーブ、スルフルラミド、ミルベメクチン、アベルメクチン、クロラントラニリプロール、ピリプロール、ブロフラニリド、フルピラジフロン、ジクロロメゾチアズ、ホウ酸、八ホウ酸二ナトリウム四水和物、ホウ砂、ホウ砂五水和物、パラジクロロベンゼン、カプリン酸などを挙げることができる。 (Insecticide, herbicide, plant growth regulator, etc.)
The pest control composition of the present invention can also be used as a composition together with an insecticide, a herbicide, a plant growth regulator and the like. These components can be used without particular limitation. The active ingredient used may be a liquid or a solid, 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 plurality of kinds of components can be used in combination.
A specific example is shown below.
Insecticides include cifluthrin, cypermethrin, deltamethrin, phenpropatrin, fenvalerate, esphenvalerate, tralomethrin, acrinathrin, bifentrin, resmethrin, tetramethrin, tefurthrin, etofenprox, ciphenotrin, permethrin, plaretrin, pyrethrin, pyrethrin, pyrethrin, pyrethrin, Pyrethroid compounds of , Dimethylbinphos, Hosalon, Chlorpyriphos, Chlorpyriphosmethyl, Pyridafenthion, Kinalphos, Metidathione, Metamidhos, Dimethate, Fermotion, Adinphosethyl, Adinphosmethyl, Salithion, Fenitrothione and other organic phosphorus compounds; , Fluphenoxuron, Flucycloxuron, Siromadin, Diafenthiuron, Hexithiazox, Novalron, Teflubenzuron, Triflumron, 4-Chloro-2- (2-Chloro-2-methylpropyl) -5- (6-iodo-3) -Pyrethylmethoxy) pyridazine-3 (2H) -one, 1- (2,6-difluorobenzoyl) -3- [2-fluoro-4- (trifluoromethyl) phenyl] urea, 1- (2,6-difluoro) Benzoyl) -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-thiadiazone-4-one, 1- (2,6-difluorobenzoyl) -3- [2-fluoro-4- (1,1,2,2-) Urea compounds such as tetrafluoroethoxy) phenyl] urea; neonicotinoid compounds such as imidacloprid, acetamipride, nitempyram, diacloden, thiamethoxam, clothianidin, thiacloprid, dinotefuran; fipronil, cartap, buprofezin, thiocyclam, benzultap, phenoxycarb , Phempyroximate, Pyridaben , Reproxifene, hydramethylnone, thiodicalve, phenobcarb, chlorphenapir, phenproximate, pimetrodin, pyrimidiphen, tebufenozide, tebufenpyrado, methoxyphenozide, triazamate, indoxacurve, sulfluramid, milbemectin, avelmectin, chloranthraniliprol , Flupyraziflon, dichloromesothiazu, boric acid, disodium octaborate tetrahydrate, borax, borax pentahydrate, paradichlorobenzene, capric acid and the like.
　除草剤としては、アトラジン、メトリブジンなどのトリアジン系化合物；フルオメツロン、イソプロチュロンなどのウレア系化合物；ブロモキシニル、アイオキシニルなどのヒドロキシベンゾニトリル系化合物；ペンディメサリン、トリフルラリンなどの２、６-ジニトロアニリン系化合物；２，４－Ｄ、ジカンバ、フルロキシピル、メコプロップなどのアリロキシアルカノイック酸系化合物；ベンスルフロンメチル、メツルフロンメチル、ニコスルフロン、プリミスルフロンメチル、シクロスルファムロンなどのスルホニルウレア系化合物；イマザピル、イマザキン、イマゼタピルなどのイミダゾリノン系化合物；ビスピリバックＮａ塩、ビスチオバックＮａ塩、アシフルオルフェンＮａ塩、サルフェントラゾン、パラコート、フルメツラム、トリフルスルフロンメチル、フェノキサプロップ－ｐ－エチル、シハロホップブチル、ジフルフェニカン、ノルフルラゾン、イソキサフルトール、グルフォシネートアンムニウム塩、グリフォセート、ベンタゾン、ベンチオカーブ、メフェナセット、プロパニル、フルチアミドなどを挙げることができる。 As herbicides, triazine compounds such as atrazine and methrividine; urea compounds such as fluometurone and isoproturon; hydroxybenzonitrile compounds such as bromoxynyl and ioxynyl; 2,6-dinitroaniline compounds such as pendimesarin and triflularin. Compounds; Allyloxy alkanoic acid compounds such as 2,4-D, dicamba, fluroxypyll, mecoprop; sulfonylurea compounds such as benzulflonmethyl, meturfuronmethyl, nicosulfone, primisulfuronmethyl, cyclosulfamron; imazapill , Imazakin, imidazolinone compounds such as imazetapill; bispyrivac Na salt, bisthiobac Na salt, asifluorphen Na salt, sulfentrazone, paracoat, flumethuram, triflusulfuronmethyl, phenoxaprop-p-ethyl, sihalohop Examples thereof include butyl, difluphenican, norflurazone, isoxaflutol, glufosinate anmnium salt, glyphosate, bentazone, benocarb, mephenacet, compound, fluthamide and the like.
　植物成長調節剤としては、マレイックヒドラジド、クロルメカット、エテフォン、ジベレリン、メピカットクロライド、チジアズロン、イナベンファイド、パクロブトラゾール、ウニコナゾールなどを挙げることができる。昆虫忌避剤としては、１Ｓ，３Ｒ，４Ｒ，６Ｒ－カラン－３、４－ジオール、ジプロピル ２，５－ピリジンジカルボキシレートなどを挙げることができる。 Examples of plant growth regulators include maleic hydrazide, chlormecut, etefon, gibberellin, mepicat chloride, tidiazulone, inabenfide, paclobutrazol, and uniconazole. Examples of the insect repellent include 1S, 3R, 4R, 6R-curan-3,4-diol, dipropyl 2,5-pyridinedicarboxylate and the like.
（重合開始剤）
　樹脂として熱又は光硬化性樹脂を用いる場合は、重合開始剤を含んでいてもよい。重合開始剤としては、光重合開始剤や熱重合開始剤を挙げることができる。 (Polymer initiator)
When a heat or photocurable resin is used as the resin, a polymerization initiator may be contained. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator.
　本発明で用いうる光重合開始剤としては、例えば、４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン［ダロキュアー２９５９：メルク社製］、α－ヒドロキシ－α，α' －ジメチルアセトフェノン［ダロキュアー１１７３：メルク社製］、メトキシアセトフェノン、２，２'－ジメトキシ－２－フェニルアセトフェノン［イルガキュア－６５１］などのアセトフェノン系開始剤；ベンゾインエチルエーテル、ベンゾインイソプロピルエーテルなどのベンゾインエーテル系開始剤；その他、ハロゲン化ケトン、アシルホスフィノキシド、アシルホスフォナートなどを例示することができる。 Examples of the photopolymerization initiator that can be used in the present invention include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [DaroCure 2959: manufactured by Merck], α-hydroxy-α, α'. -Acetophenone-based initiators such as dimethylacetophenone [Darocure 1173: manufactured by Merck], methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651]; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether. Initiators; other examples include halogenated ketones, acylphosphinoxides, acylphosphonates and the like.
　本発明で用いうる熱重合開始剤には、アゾ系の開始剤及び過酸化物系の開始剤がある。 Thermal polymerization initiators that can be used in the present invention include azo-based initiators and peroxide-based initiators.
　アゾ系の開始剤としては、例えば、アゾビス（イソブチロニトリル）、１，１'－アゾビス（シクロヘキサン－１－カルボニトリル）、２，２'－アゾビス｛２－メチル－Ｎ－［１，１－ビス（ヒドロキシメチル）エチル］プロピオンアミド｝、２、２'－アゾビス［２－メチル－Ｎ－（２－ヒロキシエチル）プロピオンアミド］、２、２'－アゾビス［２－（ヒドロキシメチル）プロピオニトリル］、２，２'－アゾビス（２、４－ジメチルバレロニトリル）、２，２'－アゾビス（４－メトキシ－２、４－ジメチルバレロニトリル）、２，２'－アゾビス（イソ酪酸ジメチル）、２，２'－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］、２，２'－アゾビス｛２－メチル－Ｎ－［１、１－ビス（ヒドロキシメチル）－２－ヒドロキシエチル］プロピオンアミド｝などを例示することができる。これらのうち、コストや汎用性の点からアゾビス（イソブチロニトリル）が好ましい。 Examples of the azo-based initiator include azobis (isobutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), and 2,2'-azobis {2-methyl-N- [1,1. -Bis (hydroxymethyl) ethyl] propionamide}, 2, 2'-azobis [2-methyl-N- (2-heroxyethyl) propionamide], 2, 2'-azobis [2- (hydroxymethyl) propionitrile ], 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (dimethyl isobutyrate), 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] Propionamide} and the like can be exemplified. Of these, azobis (isobutyronitrile) is preferable from the viewpoint of cost and versatility.
　過酸化物系の開始剤としては、半減期が１０時間となる温度が８０℃以下の比較的分解しやすいものが好ましく、例えば、ベンゾイルパーオキサイド、イソブチリルパーオキサイド、クミルペルオキシオクトエートなどを例示することができる。過酸化物系の開始剤としては、熱重合時間が短く、重合前の反応性組成物として安定なものを適宜選択することができる。 The peroxide-based initiator preferably has a half-life of 10 hours and a temperature of 80 ° C. or lower, which is relatively easily decomposed. It can be exemplified. As the peroxide-based initiator, one that has a short thermal polymerization time and is stable as a reactive composition before polymerization can be appropriately selected.
　このような重合開始剤は、硬化性樹脂の総和１００重量部に対して、０．００１～５重量部の範囲で配合される。好ましくは、０．０１～１重量部の範囲で配合される。 Such a polymerization initiator is blended in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable resin. Preferably, it is blended in the range of 0.01 to 1 part by weight.
（４）有害生物防除用組成物の製造方法
　本発明の有害生物防除用組成物は、チアベンダゾール含有配位高分子を作成してそのまま使用することができる。必要に応じて、チアベンダゾール含有配位高分子を作成後、樹脂等の他の成分と混合する。
　混合方法は、従来から知られている方法で混合することができるが、例えば、樹脂を使用する場合は、溶融混練することにより製造できる。具体的には、熱可塑性樹脂、チアベンダゾール含有配位高分子及び必要に応じて配合されるその他の添加成分を所定量秤量し、タンブラーやヘンシェルミキサーなどの各種混合機を用いて混合した後、バンバリーミキサー、ロール、プラペンダー、単軸混練押出機、二軸混練押出機、ニーダーなどを用いて溶融混練する方法が挙げられる。 (4) Method for Producing Pest Control Composition The pest control composition of the present invention can be used as it is by producing a thiabendazole-containing coordination polymer. If necessary, the thiabendazole-containing coordination polymer is prepared and then mixed with other components such as resin.
As a mixing method, a conventionally known method can be used for mixing, but for example, when a resin is used, it can be produced by melt-kneading. Specifically, a thermoplastic resin, a coordination polymer containing thiabendazole, and other additive components to be blended as necessary are weighed in a predetermined amount, mixed using various mixers such as a tumbler and a henschel mixer, and then Banbury. Examples thereof include a method of melt-kneading using a mixer, a roll, a plastic pender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader and the like.
　本発明に係る樹脂を含む有害生物防除用組成物は、主に各種製品（成形品）の製造（成形）用樹脂材料として使用される。その成形方法としては、熱可塑性樹脂材料から成形品を成形する従来から知られている方法が、制限なく適用できる。具体的には、一般的な射出成形法、超高速射出成形法、射出圧縮成形法、二色成形法、ガスアシストなどの中空成形法、断熱金型を用いた成形法、急速加熱金型を用いた成形法、発泡成形（超臨界流体も含む）、インサート成形、インモールドコーティング（ＩＭＣ）成形法、押出成形法、シート成形法、熱成形法、回転成形法、積層成形法、プレス成形法などが挙げられる。 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 products). As the molding method, a conventionally known method of molding a molded product from a thermoplastic resin material can be applied without limitation. Specifically, general injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold Molding method used, foam molding (including supercritical fluid), insert molding, in-mold coating (IMC) molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method. And so on.
　本発明の有害生物防除用組成物におけるチアベンダゾール含有配位高分子の混合量は、特に制限されない。混合するものによって適宜変更することができる。 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 changed as appropriate depending on what is mixed.
　樹脂を用いる場合、樹脂の混合量は特に制限されないが、好ましくはチアベンダゾール含有配位高分子１重量部に対して、１～１０００重量部である。好ましくは１～３００重量部である。 When a resin is used, the mixing amount of the resin is not particularly limited, but is preferably 1 to 1000 parts by weight with respect to 1 part by weight of the coordination polymer containing thiabendazole. It is preferably 1 to 300 parts by weight.
　溶媒を用いる場合、溶媒の混合量は特に制限されないが、好ましくはチアベンダゾール含有配位高分子１重量部に対して、１～１０００重量部である。好ましくは２～１００重量部である。 When a solvent is used, the mixing amount of the solvent is not particularly limited, but is preferably 1 to 1000 parts by weight with respect to 1 part by weight of the coordination polymer containing thiabendazole. It is preferably 2 to 100 parts by weight.
　本発明に係る樹脂を含む有害生物防除用組成物及びその成型品は、抗菌活性、防黴活性、抗ウイルス活性などの抗微生物活性を示す。そのため、抗微生物性を要求される用途、例えば、スプレー容器、台所用品など水周り製品、食品包装材料、カバークロス、生ゴミ用カバーなどのハウスホールド製品；ゴム製履物などのサニテーション製品；浴室の内装、フロアマット、壁用シート、壁紙、障子紙、床材、シーリング剤、接着剤、塗料などの建材；樹脂系サイディング、窯業系サイディング、タイル等の建築物の外装材；おむつ、ナプキン、失禁パット等の吸収性繊維製品、ガウン、術衣等の医療衛生製品；使い捨てトイレ、トイレ用カバー等のトイレ製品；ペットシート、ペット用おむつ、ペット用タオル等のペット用品；空気清浄機フィルター、エアコン、加湿器、除湿器などの家電製品材料；包装容器、飲食品パッケージ；医薬品包装材料、目薬容器、コンタクトレンズ、メガネレンズ、眼内レンズ、口腔内治療具などの歯科用・医療用材料寝具、靴下、下着などの繊維製品；パソコン外装材料、タブレット端末の外装材料などの筐体部材；ファンデーション容器などの化粧品材料；幼児用玩具；文房具；玩具；携帯電話・スマートホンの表面フィルム材；水濾過材料；キーボード、マウス、手すり、押しボタンなどの人間が触れる材料などに好適に用いることができる。 The pest control composition containing the resin according to the present invention and its molded product exhibit antimicrobial activity such as antibacterial activity, antibacterial activity, and antiviral activity. Therefore, applications that require anti-microbial properties, such as water-related products such as spray containers and kitchen utensils, food packaging materials, cover cloths, household products such as garbage covers; sanitary products such as rubber footwear; bathrooms. Interiors, floor mats, wall sheets, wallpaper, obstacle paper, flooring materials, sealants, adhesives, paints and other building materials; resin siding, ceramic siding, tiles and other building exterior materials; diapers, napkins, Absorbent textile products such as incontinence pads, medical hygiene products such as gowns and surgical gowns; toilet products such as disposable toilets and toilet covers; pet supplies such as pet sheets, pet diapers, and pet towels; air purifier filters, Home appliances materials such as air conditioners, humidifiers and dehumidifiers; packaging containers, food and beverage packages; pharmaceutical packaging materials, eye medicine containers, contact lenses, eyeglass lenses, intraocular lenses, oral treatment tools and other dental and medical materials bedding , Socks, underwear and other textile products; PC exterior materials, tablet terminal exterior materials and other housing materials; Foundation containers and other cosmetic materials; Toddler toys; Stationery; Toys; Mobile phone / smartphone surface film materials; Water Filtering material; It can be suitably used for materials touched by humans such as keyboards, mice, handrails, and push buttons.
　この他、本発明の有害生物防除用組成物は、塗料、顔料、インク、繊維、パルプ、ゴム、ラテックス、接着剤、フィルム、配合物、セラミック材料、金属加工油から選ばれる少なくとも一つとの組成物としても、好ましく用いることができる。
　繊維としては、例えば天然繊維｛綿、麻などの植物繊維；絹、羊毛、兎毛、アルパカ、羽毛などの動物繊維；石綿などの鉱物繊維｝、
　化学繊維｛合成繊維（ナイロン、アラミド繊維などのポリアミド系；ビニロンなどのポリビニルアルコール系；ビニリデンなどのポリ塩化ビニリデン系；ポリ塩化ビニルなどのポリ塩化ビニル系；ポリエステルなどのポリエステル系；ポリアクリロニトリル繊維、モダクリル繊維などのポリアクリロニトリル系；ポリエチレン繊維、ポリプロピレン繊維、ポリスチレン繊維などのポリオレフィン系；ポリウレタンなどのポリウレタン系；ポリクラールなどのポリクラール系；フッ素繊維などのポリフルオロエチレン系；ノボロイドなどのフェノール系；レクセ、サクセスなどのポリエーテルエステル系；ポリ乳酸繊維などのポリ乳酸系；ベンゾエートなどのポリアルキレンパラオキシベンゾエート系；ポリテトラフルオロエチレン系；ポリ青化ビニリデン系；ポリ尿素系）、
　再生繊維（レーヨン、ビスコースレーヨン、ポリノジック、キュプラ、テンセル、リヨセルなどのセルロース系；銅アンモニアレーヨンなどの銅アンモニア系；カゼイン繊維、植物性タンパク繊維、再生絹糸などのタンパク質系；アルギン繊維；キチン繊維；マンナン繊維；ゴム繊維）
　半合成繊維（アセテート、トリアセテート、酸化アセテートなどのセルロース系；プロミックスなどのタンパク質系；塩化ゴム；塩酸ゴム）
　無機繊維（グラスファイバーなどのガラス繊維；カーボンファイバーなどの炭素繊維；金属繊維；シリカ繊維、アルミナ繊維などのセラミック繊維）｝
　などに、特に好適に用いることができる。 In addition, the pest control composition of the present invention has a composition with at least one selected from paints, pigments, inks, fibers, pulps, rubbers, latexes, adhesives, films, formulations, ceramic materials, and metalworking oils. It can also be preferably used as a product.
Examples of 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 fiber {Synthetic fiber (polyamide-based such as nylon and aramid fiber; 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 fiber, Polyacrylonitrile-based such as modacryl fiber; Polyester-based such as polyethylene fiber, polypropylene fiber, and polystyrene fiber; Polyurethane-based such as polyurethane; Polyclaral-based such as polyclaral; Polyfluoroethylene-based such as fluorine fiber; Polyester ester type such as success; Polylactic acid type such as polylactic acid fiber; Polyalkylene paraoxybenzoate type such as benzoate; Polytetrafluoroethylene type; Polyblue vinylidene type; Polyurea type),
Regenerated fiber (cellulose-based such as rayon, biscoast rayon, polynosic, cupra, tencel, lyocell; cuprammonium-based such as cuprammonium rayon; protein-based such as casein fiber, vegetable protein fiber, regenerated silk thread; argin fiber; chitin fiber Rayon fiber; rubber fiber)
Semi-synthetic fiber (cellulose type such as acetate, triacetate, oxide acetate; protein type such as Promix; rubber chloride; rubber hydrochloride)
Inorganic fiber (glass fiber such as glass fiber; carbon fiber such as carbon fiber; metal fiber; ceramic fiber such as silica fiber and alumina fiber)}
It can be particularly preferably used for such purposes.
　本発明において、対象とする繊維製品の形態としては、糸、紐、ロープ、生地（織地、編地、不織布）等があげられる。
　具体的な例としては、シーツ、枕カバー、タオルなどのリネン品；パジャマ、白衣、エプロン、帽子、ユニフォーム、制服などの各種衣料品；鞄、靴などの服飾雑貨；カーシート、椅子、ベビーカーなどの座席用シートおよびそのシートカバー；カーテン、壁紙などの内装材；空調フィルタ、掃除機フィルタなどのフィルタ類；テント、寝袋などのアウトドア用品；マスクなどの衛生用品；冷蔵庫内用シート、冷凍庫カバーなど、家庭用品や産業用資材に広く用いることができる。 In the present invention, examples of the form of the target textile product include threads, strings, ropes, fabrics (woven fabrics, knitted fabrics, non-woven fabrics) and the like.
Specific examples include linen items such as sheets, pillowcases and towels; various clothing items such as pajamas, white clothes, aprons, hats, uniforms and uniforms; fashion accessories such as bags and shoes; car seats, chairs, strollers, etc. Seats and their seat covers; Interior materials such as curtains and wallpaper; Filters such as air conditioning filters and vacuum cleaner filters; Outdoor products such as tents and sleeping bags; Sanitary products such as masks; Seats for refrigerators, freezer covers, etc. , Can be widely used for household goods and industrial materials.
　本発明に係る有害生物防除用組成物は、抗菌活性、防黴活性、抗ウイルス活性などの抗微生物活性を示す。そのため、抗微生物性を要求される各種材料であれば、好適に用いることができる。 The pest control composition according to the present invention exhibits antimicrobial activity such as antibacterial activity, antibacterial activity, and antiviral activity. Therefore, any material that requires antimicrobial properties can be suitably used.
　以下に、実施例を示すが、本発明の技術的範囲は、これらに限定されない。 Examples are shown below, but the technical scope of the present invention is not limited thereto.
実施例１：[Zn(TBZ)(BDC)]ｎの配位高分子（以下、単に「Zn(TBZ)(BDC)」という）
　110 mlガラスバイアルにチアベンダゾール：TBZ (0.403 g, 2 mmol)、テレフタル酸：BDC (0.332 g, 2mmol)、塩化亜鉛 (0.273 g, 2 mmol)のDMF (48 ml)懸濁液を密閉し、130℃で48時間静置して反応を行った。反応後、130℃から室温まで50時間かけてゆっくりと冷却することで、単結晶を得た。
　得られた単結晶について、測定装置Ｂｒｕｋｅｒ　Ｄ２ＰＨＡＳＥＲを用いて、ＣｕＫα線にて粉末Ｘ線回折パターンを測定したところ、5°～50°までの粉末Ｘ線測定において、図１の様な回折パターンを示した。

（粉末Ｘ線回折パターン）
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
Example 1: [Zn (TBZ) (BDC)] n coordination polymer (hereinafter, simply referred to as “Zn (TBZ) (BDC)”)
A 110 ml glass vial was sealed with a DMF (48 ml) suspension of thiabendazole: TBZ (0.403 g, 2 mmol), terephthalic acid: BDC (0.332 g, 2 mmol), zinc chloride (0.273 g, 2 mmol) and 130. The reaction was carried out by allowing it to stand at ° C for 48 hours. After the reaction, a single crystal was obtained by slowly cooling from 130 ° C. to room temperature over 50 hours.
When the powder X-ray diffraction pattern of the obtained single crystal was measured by CuKα ray using the measuring device Bruker D2PHASER, the diffraction pattern as shown in FIG. 1 was obtained in the powder X-ray measurement from 5 ° to 50 °. Indicated.

(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. 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
　実施例１で得たられた単結晶についてＸ線構造解析を行った結果、Zn(TBZ)(BDC)で表される一次元鎖状構造の配位高分子であることが確認された。Ｘ線構造解析における空間情報を表１に、分子モデルを図２に示す。 As a result of X-ray structure analysis of the single crystal obtained in Example 1, it was confirmed that it is a coordination polymer having 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 FIG.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
（他の測定結果）
　実施例１で得た結晶について、赤外分光光度計（FT-IR）による測定結果を図７に示す。
　また、実施例１で得た結晶について、13C-CPMAS-NMR測定結果を図８に示す。 (Other measurement results)
FIG. 7 shows the measurement results of the crystal obtained in Example 1 by an infrared spectrophotometer (FT-IR).
The 13C-CPMAS-NMR measurement results of the crystals obtained in Example 1 are shown in FIG.
実施例２：[Zn4(TBZ)2(BDC)3・6DMF]ｎの配位高分子 （以下、単に「Zn4(TBZ)2(BDC)3・6DMF」という）
　実施例１の塩化亜鉛を硝酸亜鉛6水和物 (0.595 g, 2 mmol)に変更し、他は同様の条件で反応を行った。 Example 2: [Zn 4 (TBZ) 2 (BDC) 3.6DMF ] n coordination polymer (hereinafter, simply referred to as “Zn 4 (TBZ) 2 (BDC) 3.6DMF ”)
The zinc chloride of Example 1 was changed to zinc nitrate hexahydrate (0.595 g, 2 mmol), and the other reactions were carried out under the same conditions.
　実施例２で得られた単結晶についてＸ線構造解析を行った結果、Zn4(TBZ)2(BDC)3・6DMFで表される各構成単位がネットワーク状に繋がり、一次元チャネル空孔を有する配位高分子であることが確認された。Zn4(TBZ)2(BDC)3・6DMFとは、Zn4(TBZ)2(BDC)3空孔内に単位当たり６分子のDMFが取り込まれていることを表す。Ｘ線構造解析における空間情報を表２に、分子モデルを図３に示す。 As a result of X-ray structure analysis of the single crystal obtained in Example 2, each structural unit represented by Zn 4 (TBZ) 2 (BDC) 3.6 DMF is connected in a network to form a one-dimensional channel hole. It was confirmed that it is a coordination polymer having. Zn 4 (TBZ) 2 (BDC) 3・ 6DMF means that 6 molecules of DMF per unit are incorporated into Zn 4 (TBZ) 2 (BDC) 3 pores. The spatial information in the X-ray structure analysis is shown in Table 2, and the molecular model is shown in FIG.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　その後、150℃の環境下にサンプルZn4(TBZ)2(BDC)3・6DMFを静置し、真空ポンプで減圧乾燥することで、溶媒（DMF）除去を行った。
　溶媒除去前後の単結晶について、測定装置Ｂｒｕｋｅｒ　Ｄ２ＰＨＡＳＥＲを用いて、ＣｕＫα線にて粉末Ｘ線回折パターンを測定した。
　5°～50°までの粉末Ｘ線測定において、図４の様な回折パターンを示した。
　溶媒を除去することで、粉末Ｘ線回折パターンに僅かな差異が認められた。溶媒除去前後では、格子のゆがみ解消等による面間隔の変化が生じるが、骨格への影響は少ないことが推察された。

（粉末Ｘ線回折パターン）
Zn4(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

Zn4(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 Then, the sample Zn 4 (TBZ) 2 (BDC) 3.6 DMF 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 the solvent was removed, the powder X-ray diffraction pattern was measured with CuKα rays using the measuring device Bruker D2PHASER.
In the powder X-ray measurement from 5 ° to 50 °, the diffraction pattern as shown in FIG. 4 was shown.
By removing the solvent, a slight difference was observed in the powder X-ray diffraction pattern. Before and after the solvent was removed, the surface spacing changed due to the elimination of lattice distortion, but it was inferred that the effect 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
（熱分析）
　実施例１および２において得られた試料及びＴＢＺ（比較例）について、メノウ鉢で粉砕後、ＴＧ－ＤＳＣ（熱分析装置）「メトラートレドＴＧＡ-ＤＳＣ３+」により測定した。結果を図５に示す。
　加熱温度の上昇に伴う重量減少は、実施例１および２はいずれも、比較例に比して顕著に遅いことを示した。 (Thermal analysis)
The samples and TBZ (Comparative Example) obtained in Examples 1 and 2 were pulverized in an agate pot and then measured by TG-DSC (thermal analyzer) "METLATER Toledo TGA-DSC3 +". The results are shown in FIG.
The weight loss with increasing heating temperature was shown to be significantly slower in both Examples 1 and 2 as compared with Comparative Examples.
(溶解度試験)
　実施例１で得られた試料１０ mgを蒸留水５０ mLに添加して飽和状態にし、撹拌子により、一定時間室温で撹拌後、フィルターろ過(０．２um)してＨＰＬＣ分析を行い、水溶解度を算出した。
　結果、水溶解度はZn(TBZ)(BDC)が１３．４ｐｐｍ、Zn４(TBZ)２(BDC)３が１．３ｐｐｍであり、TBZ　２０．４ｐｐｍと比較して、大きく低下していた。
　水への溶解性が低下することで、水が介在する使用場面においては特に、有効成分の溶出量が抑制されることとなり、より長期間の効力維持が期待できる。 (Solubility test)
10 mg of the sample obtained in Example 1 was added to 50 mL of distilled water to saturate it, and after stirring at room temperature for a certain period of time with a stirrer, filter filtration (0.2 um) was performed for HPLC analysis, and water solubility was performed. Was calculated.
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 those of TBZ 20.4 ppm.
By reducing the solubility in water, the amount of the active ingredient eluted is suppressed, especially in the case of use in which water is present, and it can be expected that the efficacy will be maintained for a longer period of time.
（細菌ＭＩＣ試験・カビＭＩＣ試験）
　ノニオン性界面活性剤ペネロールN-100を添加した薬液（Zn(TBZ)(BDC)（実施例１）、Zn４(TBZ)２(BDC)３（実施例２）及びTBZ、BDC、ZnCl２、Zn(NO３)２）を所定の濃度に希釈し、この希釈薬液を９６穴プレートウェルに分注して、以下の条件で細菌ＭＩＣ試験およびカビＭＩＣ試験を行った。
　細菌ＭＩＣ試験：培養したバクテリア（Ｅｓｃｈｅｒｉｃｈｉａ　ｃｏｌｉ、Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ　ａｕｒｅｕｓ　ｓｕｂｓｐ．　ａｕｒｅｕｓ）の接種液を、薬液を分注した９６穴プレートウェルに滴下した。31℃、暗所で24時間静置培養し、バクテリアの増殖が認められない最低の濃度であるMIC(最小発育阻止濃度)(mg/L)を求めた。結果を表３に示す。
　カビＭＩＣ試験：培養して得た胞子及び菌糸（Ａｓｐｅｒｇｉｌｌｕｓ　ｎｉｇｅｒ，Ｔｒｉｃｈｏｄｅｒｍａ　ｖｉｒｅｎｓ）を分散した接種液を、薬液を分注した９６穴プレートウェルに滴下した。２６℃、暗所で７日間静置培養し、カビの増殖が認められない最低の濃度であるMIC(最小発育阻止濃度)(mg/L)を求めた。結果を表３に示す。 (Bacterial MIC test / Mold MIC test)
Chemical solutions to which the nonionic surfactant Penelol N-100 was added (Zn (TBZ) (BDC) (Example 1), Zn 4 (TBZ) 2 (BDC) 3 (Example 2) and TBZ, BDC, ZnCl 2 , Zn (NO 3 ) 2 ) was diluted to a predetermined concentration, and this diluted drug solution was dispensed into a 96-well plate well, and a bacterial MIC test and a mold MIC test were performed under the following conditions.
Bacterial MIC test: An inoculum of cultured bacteria (Escherichia coli, Staphylococcus aureus subsp. Aureus) was added dropwise to a 96-well plate well in which the drug solution was dispensed. The MIC (minimum inhibitory concentration) (mg / L), which is the lowest concentration at which bacterial growth is not observed, was determined by statically culturing in a dark place at 31 ° C for 24 hours. 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 a 96-well plate well to which the drug solution was dispensed. The MIC (minimum inhibitory concentration) (mg / L), which is the lowest concentration at which mold growth is not observed, was determined by statically culturing in a dark place at 26 ° C. for 7 days. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　ＭＩＣ試験において、実施例１及び２にて得られた試料は、いずれも良好な抗菌活性及び防カビ活性を示した。
　チアベンダゾール、テレフタル酸及び亜鉛からなる配位高分子とすることで、亜鉛及びチアベンダゾールそれぞれが適宜適当量放出されることにより、各成分が標的とする有害生物に対して、良好な効果を発揮することが示唆される。 In the MIC test, the samples obtained in Examples 1 and 2 both showed good antibacterial activity and antifungal activity.
By using a coordination polymer consisting of thiabendazole, terephthalic acid and zinc, zinc and thiabendazole are each released in appropriate amounts in appropriate amounts, and each component exerts a good effect on the target pests. Is suggested.
（ポリカーボネート樹脂練り込み後の耐候試験）
　Zn(TBZ)(BDC)（実施例１）及びTBZの各成分を、TBZの含有量が１％となるように、それぞれ芳香族ポリカーボネート樹脂（「ユーピロンS-2000」三菱エンジニアリングプラスチックス(株)製）と混合した後、二軸混練押出機（同方向回転二軸混練押出機ＨＫ-２５Ｄ(４１Ｄ)(株)パーカーコーポレーション製）に供給し、スクリュー回転数１５０ｒｐｍ 、混練温度２７０℃(実測樹脂温度２９０℃)の条件で混練し、ペレタイザーを用いてペレット化して、Zn(TBZ)(BDC)（実施例１）及びTBZそれぞれの芳香族ポリカーボネート樹脂組成物のペレットを得た。
　上記ペレットならびに薬剤無添加（ＢＬ）のペレットを１００℃で乾燥させた後、それぞれ射出成形機（小型電動射出成形機　ＳＥ１８ＤＵＺ　住友重機械工業(株)製）にて、シリンダー温度２７０～２９０℃ 、金型温度８０℃、成形サイクル４０秒または３００秒の条件で射出成形を行い、４０×４０×２ｍｍ厚みのプレート試験片を作製した。
　得られたプレート試験片を用いて、スーパーキセノンウェザーメーターによる耐侯処理（紫外線強度：１８０ W/m2、処理時間：１００h）を実施した。結果を図６に示す。ＴＢＺを練り込んだ樹脂に比べて、Zn (TBZ) (BDC)を練り込んだ樹脂は、黄味が抑えられている。 (Weather resistance test after kneading polycarbonate resin)
Each component of Zn (TBZ) (BDC) (Example 1) and TBZ is an aromatic polycarbonate resin ("Iupilon S-2000" Mitsubishi Engineering Plastics Co., Ltd. so that the content of TBZ is 1%. After mixing with (manufactured), it is supplied to a twin-screw kneading extruder (same-direction rotating twin-screw kneading extruder HK-25D (41D) manufactured by Parker Corporation), screw rotation speed 150 rpm, kneading temperature 270 ° C (actual measurement resin). The mixture was kneaded at a temperature of 290 ° C.) and pelletized using a pelletizer to obtain pellets of Zn (TBZ) (BDC) (Example 1) and TBZ aromatic polycarbonate resin compositions.
After drying the above pellets and the chemical-free (BL) pellets at 100 ° C, each injection molding machine (small electric injection molding machine SE18DUZ manufactured by Sumitomo Heavy Industries, Ltd.) has a cylinder temperature of 270 to 290 ° C. Injection molding was performed under the conditions of a mold temperature of 80 ° C. and a molding cycle of 40 seconds or 300 seconds to prepare a plate test piece having a thickness of 40 × 40 × 2 mm.
Using the obtained plate test piece, weather resistance treatment (ultraviolet intensity: 180 W / m 2 , treatment time: 100 h) with a super xenon weather meter was carried out. The results are shown in FIG. Compared with the resin kneaded with TBZ, the resin kneaded with Zn (TBZ) (BDC) has less yellowness.
（プレート試験片による抗菌試験）
　上記耐候試験で得られたプレート試験片（スーパーキセノンウェザーメーターによる耐侯処理なし）を用いて、抗菌試験を行った。
　ＪＩＳ－Ｚ－２８０１に準拠し、供試菌としてＥｓｃｈｅｒｉｃｈｉａ　ｃｏｌｉおよびＳｔａｐｈｙｌｏｃｏｃｃｕｓ　ａｕｒｅｕｓ　ｓｕｂｓｐ．　ａｕｒｅｕｓを使用した。
　プラスチックシャーレに試験片を置き、普通寒天培地で前培養した試験菌を、それぞれＮＢ培地で希釈して接種用菌液とし、試料上に滴下し、フィルムを被せ、恒温恒湿器（３５±１℃、相対湿度９５％）にて、培養した。
　２４時間後、ＳＣＤＬＰ培地を用いて試験片表面およびフィルムを洗い出した。洗い出した液１ｍｌ当たりの菌数を、普通寒天培地を用いて寒天平板培養法により算出し、試料１ｃｍ2あたりの菌数を求めた。
　抗菌試験結果を表４に示す。Zn(TBZ)(BDC)はＢＬ（ブランク）に対して抗菌活性値２以上となり、抗菌効果が認められた。 (Antibacterial test using plate test piece)
An antibacterial test was performed using a plate test piece (without weather resistance treatment with a super xenon weather meter) obtained in the above weather resistance test.
According to JIS-Z-2801, Escherichia coli and Staphylococcus aureus subsp. aureus was used.
Place the test piece on a plastic petri dish, dilute the test bacteria pre-cultured on a normal agar medium with NB medium to obtain a bacterial solution for inoculation, drop it on the sample, cover it with a film, and place it in a constant temperature and humidity chamber (35 ± 1). Cultivated at ° C. and relative humidity 95%).
After 24 hours, the surface of the test piece and the film were washed out using SCDLP medium. The number of bacteria per 1 ml of the washed-out solution was calculated by the agar plate culture method using a normal agar medium, and the number of bacteria per 1 cm 2 of the sample 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.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　高温での成形が必要となるポリカーボネート樹脂への練り込みにおいても、Zn(TBZ)(BDC)は耐熱性に優れるため、有効であることが示された。 It was shown that Zn (TBZ) (BDC) is effective even in kneading into polycarbonate resin, which requires molding at high temperature, because it has excellent heat resistance.
（プレート試験片による防カビ試験）
　上記耐候試験で得られたプレート試験片（スーパーキセノンウェザーメーターによる耐侯処理後）を用いて、防カビ試験を行った。
　防カビ試験は、ＪＩＳ Ｚ ２９１１：２０１８ 附属書Ａ　プラスチック製品の試験Ｂ法に従った。グルコース添加無機塩寒天培地にそれぞれの試験片を置床し、Ａｓｐｅｒｇｉｌｌｕｓ　ｎｉｇｅｒ，Ｐｅｎｉｃｉｌｌｉｕｍ　ｐｉｎｏｐｈｉｌｕｍ，Ｐａｅｃｉｌｏｍｙｃｅｓ　ｖａｒｉｏｔｉｉ，Ｔｒｉｃｈｏｄｅｒｍａ　ｖｉｒｅｎｓ，Ｃｈａｅｔｏｍｉｕｍ　ｇｌｏｂｏｓｕｍの混合胞子懸濁液を噴霧し、２９℃にて培養した。
　一定時間後、試料上のカビ発生を下記の基準に基づいて６段階（０：肉眼及び顕微鏡下でカビの発生なし～５：試料全体を菌糸が覆っているのが肉眼で確認される）で評価した。
　スーパーキセノンウェザーメーターによる耐侯処理後のプレート試験片を用いた防カビ試験の結果を表５に示す。試験開始後４週間において、TBZを練り込んだポリカーボネート樹脂と比較してZn(TBZ)(BDC)を練りこんだものは、カビの発生が抑制された。 (Anti-mold test using plate test pieces)
An antifungal test was carried out using the plate test piece (after the weather resistance treatment with a super xenon weather meter) obtained in the above weather resistance test.
The antifungal test was carried out according to JIS Z 2911: 2018, Annex A, Test B method for plastic products. Each test piece was placed on a glucose-added inorganic salt agar medium, and a mixed spore suspension of Aspergillus niger, Paecilomyces variotii, Trichoderma virens, and Chaetomium globosum was sprayed.
After a certain period of time, mold growth on the sample is performed in 6 stages based on the following criteria (0: no mold growth with the naked eye and under a microscope-5: it is confirmed with the naked eye that the entire sample is covered with hyphae). evaluated.
Table 5 shows the results of the antifungal test using the plate test piece after the weather resistance treatment with the super xenon weather meter. In the 4 weeks after the start of the test, the growth of mold was suppressed in the one in which Zn (TBZ) (BDC) was kneaded as compared with the polycarbonate resin in which TBZ was kneaded.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　Zn(TBZ)(BDC)は、耐候性の面でも優れていることが示された。 It was shown that Zn (TBZ) (BDC) is also excellent in terms of weather resistance.
　チアベンダゾール、テレフタル酸及び亜鉛を含有する配位高分子は、光や熱による色調変化が軽減された、かつ、高熱をかけても分解しにくく、水に溶脱しにくい、耐候性に優れたものである。防カビ用途や抗菌用途等の有害生物防除に、広く用いることができる。 Coordination polymers containing thiabendazole, terephthalic acid, and zinc have excellent weather resistance, with reduced color change due to light and heat, less decomposition even when exposed to high heat, and less leaching into water. be. It can be widely used for controlling harmful organisms such as antifungal and antibacterial applications.
（ハードコート塗膜による抗ウイルス試験）
　ハードコート塗膜を作成し、バクテリオファージQβに対する効力を確認した。 (Antiviral test with hard coat coating film)
A hard-coated coating film was prepared and its efficacy against bacteriophage Qβ was confirmed.
塗膜作成
自動塗工装置（テスター産業社製ＰＩ-１２１０）を用いて、東レ社製の二軸延伸ポリエステル（ＰＥＴ）フィルム（ルミラー(Ｒ)フィルム　T60透明　２５０μm　１４８×２１０mm）に塗膜材料液（エタノール　８１．０６、ＫＢＭ-５０３（信越化学工業社製） ８．７４、オルガノシリカゾルＩＰＡ－ＳＴ（日産化学工業社製）　3.5、2-メチル-4'-(メチルチオ)-2-モルホリノプロピオフェノン　0.2、Aluminum acetylacetonate　１．５、Zn(TBZ)(BDC)　５ (単位：Ｗｔ%)）　約３ｍＬを塗布した。その後、１００℃の恒温槽にて1分間乾燥させ、紫外線硬化用光原装置（アイグラフィックス社製）にて、固化させた。 Coating film creation Using an automatic coating device (PI-1210 manufactured by Tester Sangyo Co., Ltd.), a biaxially stretched polyester (PET) film manufactured by Toray Industries, Inc. (Lumirror (R) film T60 transparent 250 μm 148 × 210 mm) Coating material liquid (ethanol 81.06, KBM-503 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 8.74, organosilica sol IPA-ST (manufactured by Nissan Chemical Industry Co., Ltd.) 3.5, 2-methyl-4'-(methylthio) -2 -About 3 mL of morpholinopropiophenone 0.2, Aluminum acetylacetonate 1.5, Zn (TBZ) (BDC) 5 (unit: Wt%)) was applied. Then, it was dried in a constant temperature bath at 100 ° C. for 1 minute, and solidified by an ultraviolet curing optical source device (manufactured by Eye Graphics Co., Ltd.).
抗ウイルス試験
JIS R 1756：2020「ファインセラミックス－可視光応答形光触媒材料の抗ウイルス性試験方法－バクテリオファージＱβを用いる方法」に準拠して、作成したハードコート塗膜の抗ウイルス試験を行った。但し、試験液を接種した試験片（ハードコート塗膜）への光照射は行わず、暗所に静置するのみとした。
　ハードコート塗膜にバクテリオファージを処理して4時間静置後、大腸菌を用いて、バクテリオファージ感染価を測定した。 Antiviral test
An anti-virus test was performed on the prepared hard coat coating film in accordance with JIS R 1756: 2020 "Fine Ceramics-Anti-virus test method for visible light responsive photocatalytic materials-Method using bacteriophage Qβ". However, the test piece (hard coat coating film) inoculated with the test solution was not irradiated with light, and was only allowed to stand in a dark place.
The hardcourt coating was treated with bacteriophage and allowed to stand for 4 hours, and then the bacteriophage infectivity titer was measured using Escherichia coli.
　結果、Zn(TBZ)(BDC)を添加して作成したハードコート塗膜は、Zn(TBZ)(BDC)に代えてTBZを添加して作成したハードコート塗膜と比較して、抗ウイルス活性値が高く、優れた活性が認められた。 As a result, the hard-coated coating film prepared by adding Zn (TBZ) (BDC) has antiviral activity as compared with the hard-coated coating film prepared by adding TBZ instead of Zn (TBZ) (BDC). The value was high and excellent activity was observed.

Claims (8)

  1. チアベンダゾール（ＴＢＺ）、テレフタル酸（ＢＤＣ）及び亜鉛（Ｚｎ）を含有する配位高分子。 Coordination polymer containing thiabendazole (TBZ), terephthalic acid (BDC) and zinc (Zn).
  2. 式（I）
    [Ｚｎa（ＴＢＺ）b（ＢＤＣ）cＲd]n　　　（I）
    （式中、Ｒは亜鉛イオンの対アニオンを示す。ａ，ｂ及びｃは１以上の整数、ｄは０以上の整数を示す。ｎはＺｎa（ＴＢＺ）b（ＢＤＣ）cＲdで表される構成単位の集合数であり、特に限定されない）
    で表される化合物又はその溶媒付加物である、請求項１に記載の配位高分子。     Equation (I)
    [Zn a (TBZ) b (BDC) c R d ] n (I)
    (In the formula, R indicates the counter anion of zinc ion. A, b and c indicate an integer of 1 or more, d indicates an integer of 0 or more. N is represented by Zn a (TBZ) b (BDC) c R d . It is the number of sets of constituent units to be formed, and is not particularly limited.)
    The coordination polymer according to claim 1, which is a compound represented by the above or a solvent adduct thereof.
  3. [Ｚｎ(ＴＢＺ)(ＢＤＣ)]ｎまたは [Ｚｎ４(ＴＢＺ)2(ＢＤＣ)3]ｎ（これらの式中、ｎはＺｎ(ＴＢＺ)(ＢＤＣ)またはＺｎ４(ＴＢＺ)2(ＢＤＣ)3で表される構成単位の集合数であり、特に限定されない）で表される、請求項１または２に記載の配位高分子。 [Zn (TBZ) (BDC)] n or [Zn 4 (TBZ) 2 (BDC) 3 ] n (In these equations, n is Zn (TBZ) (BDC) or Zn 4 (TBZ) 2 (BDC) 3 The coordination polymer according to claim 1 or 2, which is the number of aggregates of the structural units represented by, and is not particularly limited).
  4. 請求項１～３のいずれか１項に記載の配位高分子を含む、有害生物防除組成物。 A pest control composition comprising the coordination polymer according to any one of claims 1 to 3.
  5. 抗微生物性を有する成分、殺虫剤、除草剤、植物成長調節剤のうちのいずれか１種をさらに含むものである、請求項４に記載の有害生物防除組成物。 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. 工業製品の微生物汚染防除剤用である、請求項４または５に記載の有害生物防除組成物。 The pest control composition according to claim 4 or 5, which is used as a microbial contamination control agent for industrial products.
  7. 有害生物防除組成物が、樹脂組成物である、請求項６に記載の有害生物防除組成物。 The pest control composition according to claim 6, wherein the pest control composition is a resin composition.
  8. 有害生物防除組成物が、繊維または糸である、請求項６に記載の有害生物防除組成物。 The pest control composition according to claim 6, wherein the pest control composition is a fiber or a thread.
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Publication number Priority date Publication date Assignee Title
GB1070702A (en) * 1964-11-03 1967-06-01 Commw Scient Ind Res Org New metal chelates of substituted benzimidazoles having anthelmintic properties and the preparation thereof
JP2020029440A (en) * 2018-08-24 2020-02-27 日本曹達株式会社 Bioside composition

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WANG JIA-JUN CUI YUN-CHENG LIU LI-HUI HUANG YAN-JU LÜ MING LI CHUAN-BI GAO GUANG: "Crystal structure of a Mn(II) coordination polymer: [Mn(TP)(TBZH)2]n (TBZH = thiabendazole, TP = terephthalic acid", CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, vol. 29, no. 2, 15 February 2010 (2010-02-15), pages 240 - 244, XP055932534, DOI: 10.14102/j.cnki.0254-5861.2010.02.013 *
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