WO2015093519A1 - Disinfectant composition - Google Patents

Disinfectant composition Download PDF

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WO2015093519A1
WO2015093519A1 PCT/JP2014/083385 JP2014083385W WO2015093519A1 WO 2015093519 A1 WO2015093519 A1 WO 2015093519A1 JP 2014083385 W JP2014083385 W JP 2014083385W WO 2015093519 A1 WO2015093519 A1 WO 2015093519A1
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component
group
methyl
bromo
formula
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PCT/JP2014/083385
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陽 濱川
新井　重文
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日本曹達株式会社
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Priority to JP2015553578A priority Critical patent/JP6078170B2/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
    • A01N43/80—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 1,2

Definitions

  • the present invention relates to a fungicide composition. More specifically, the present invention relates to a fungicide composition used for controlling bacteria, molds, yeasts, algae and the like.
  • This application claims priority based on Japanese Patent Application No. 2013-263707 for which it applied to Japan on December 20, 2013, and uses the content here.
  • Microbicidal compounds having a 4-isothiazolin-3-one skeleton are collectively referred to as isothiazoline fungicides and are used to control harmful microorganisms such as bacteria, fungi, yeasts and algae.
  • isothiazoline fungicides include 2-methyl-4-isothiazolin-3-one (hereinafter sometimes abbreviated as H-MIT), 5-chloro-2-methyl-4-isothiazolin-3-one ( Hereinafter abbreviated as Cl-MIT), 1,2-benzisothiazolin-3-one (hereinafter sometimes abbreviated as BIT), 2-n-octyl-4-isothiazolin-3-one, 4 , 5-dichloro-2-octyl-4-isothiazolin-3-one, 2-n-butyl-1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazoline-3- ON (hereinafter sometimes abbreviated as MTI
  • Patent Document 1 proposes a combination of 2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitro-1,3-propanediol.
  • Patent Document 2 proposes a combination of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitro-1,3-propanediol.
  • Patent Document 3 describes an antibacterial N-formal such as hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine and a bactericide such as 2-n-octyl-4-isothiazolin-3-one. Proposes a combination.
  • An object of the present invention is to provide a new fungicide composition using 2-methyl-4,5-trimethylene-4-isothiazolin-3-one.
  • Component (A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one
  • Component (B) compound represented by formula (1), hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione, polyhexa
  • a disinfectant composition comprising methyleneguanidine hydrochloride and at least one selected from the group consisting of polyhexamethylene biguanide hydrochloride.
  • X 1 and X 2 each independently represent a bromo group, a nitro group or a cyano group, provided that at least one of X 1 and X 2 is a bromo group.
  • R 1 is methyl.
  • R 2 represents a methyl group, a hydroxymethyl group or an aminocarbonyl group.
  • the compound represented by the formula (1) is 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, or 2,2-dibromo-3-nitrilo
  • Component (B) is hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo- 2-nitroethanol, 2,2-dibromo-3-nitrilopropionamide, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione, polyhexamethyleneguanidine hydrochloride, or polyhexamethylenebiguanide hydrochloride [3] The disinfectant composition described in 1.
  • bactericidal composition having a further excellent bactericidal effect Things are provided.
  • the fungicide composition of the present invention comprises component (A): 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, component (B): a compound represented by formula (1), hexahydro- Selected from the group consisting of 1,3,5-tris (2-hydroxyethyl) -s-triazine, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione, polyhexamethylene guanidine hydrochloride, and polyhexamethylene biguanide hydrochloride And at least one of the above.
  • X 1 and X 2 each independently represent a bromo group, a nitro group or a cyano group, provided that at least one of X 1 and X 2 is a bromo group.
  • R 1 is methyl.
  • R 2 represents a methyl group, a hydroxymethyl group or an aminocarbonyl group.
  • Component (A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one is a compound represented by the formula (2).
  • One of the components (B), hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, is a compound represented by the formula (3).
  • Didecyldimethylammonium chloride which is one of the components (B), is a compound represented by the formula (4).
  • Benzalkonium chloride which is one of the components (B), is a compound represented by the formula (5).
  • Zinc pyrithione which is one of the components (B), is a compound represented by the formula (6).
  • Polyhexamethylene guanidine hydrochloride which is one of the components (B), is a compound represented by the formula (7).
  • Polyhexamethylene biguanide hydrochloride which is one of the components (B), is a compound represented by the formula (8).
  • Examples of the compound represented by the formula (1) which is one of the components (B) include 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, and 2,2 -Dibromo-3-nitrilopropionamide is preferred.
  • 2-bromo-2-nitropropane-1,3-diol is a compound represented by the formula (1a)
  • 2,2-dibromo-2-nitroethanol is a compound represented by the formula (1b
  • 2,2-Dibromo-3-nitrilopropionamide is a compound represented by the formula (1c).
  • component (B) in the fungicide composition of the present invention is not particularly limited with respect to component (A), and may vary depending on the target fungus, but component (A) 100
  • the amount is preferably 1 to 10,000 parts by mass, more preferably 2 to 900 parts by mass with respect to parts by mass.
  • the amount of the component (B) is preferably 10 150 parts by mass.
  • the amount of component (B) is preferably 150 with respect to 100 parts by mass of component (A). ⁇ 900 parts by mass.
  • the amount of component (B) is preferably based on 100 parts by mass of component (A) 20 to 500 parts by mass.
  • component (B) is at least one selected from the group consisting of polyhexamethylene guanidine hydrochloride and polyhexamethylene biguanide hydrochloride
  • the amount of component (B) is based on 100 parts by mass of component (A)
  • the amount is preferably 2 to 300 parts by mass.
  • component (B) is zinc pyrithione
  • the amount of component (B) is preferably 5 to 150 parts by mass with respect to 100 parts by mass of component (A).
  • component (B) When component (B) is 2-bromo-2-nitropropane-1,3-diol, the amount of component (B) is preferably 20 to 30 parts by mass with respect to 100 parts by mass of component (A). It is. When component (B) is 2,2-dibromo-2-nitroethanol, the amount of component (B) is preferably 20 to 80 parts by mass with respect to 100 parts by mass of component (A). When component (B) is 2,2-dibromo-3-nitrilopropionamide, the amount of component (B) is preferably 10 to 150 parts by mass with respect to 100 parts by mass of component (A).
  • the amount of component (B) is preferably 30 to 80 parts by mass with respect to 100 parts by mass of component (A).
  • the amount of the component (B) is preferably 20 to 500 parts by mass with respect to 100 parts by mass of the component (A).
  • the amount of component (B) is preferably 2 to 300 parts by mass with respect to 100 parts by mass of component (A).
  • the amount of component (B) is preferably 3 to 150 parts by mass with respect to 100 parts by mass of component (A).
  • the dosage form of the fungicide composition of the present invention is not particularly limited, but is preferably liquid at room temperature.
  • Specific examples of the liquid disinfectant composition include an aqueous solvent, a suspending agent, an emulsion, an emulsion, and a suspoemulsion. These dosage forms can be selected according to the physical properties of the sterilizing component contained and the application of the sterilizing composition.
  • the fungicide composition of the present invention may contain components such as a solvent and a surfactant as necessary.
  • Organic solvents include nonpolar solvents such as toluene, xylene, and methylnaphthalene; lower alcohols such as ethanol and isopropanol; glycol solvents such as ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and glycerin; acetone, methyl ethyl ketone, and cyclohexanone Ketone solvents such as dimethylformamide, propylene carbonate, dimethyl sulfoxide, acetonitrile, and polar solvents such as N-methylpyrrolidone.
  • nonpolar solvents such as toluene, xylene, and methylnaphthalene
  • lower alcohols such as ethanol and isopropanol
  • glycol solvents such as ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and glycerin
  • surfactant examples include cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylbenzyldimethylammonium salt, alkylpyridinium salt, and polyhexamethylene biguanide.
  • Nonionic surfactants such as ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene castor oil, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester; alkylmethylamine oxide, alkyl Examples
  • the biocidal composition of the present invention may contain other biocidal active ingredients.
  • the biocidal active ingredient include those having activities such as microbicidal properties, antiseptic properties, fungicidal properties, algal-proofing properties, ant-proofing properties, and insecticidal properties.
  • the fungicide composition of the present invention has a wide range of control targets and can be stored for a long period of time, or a further synergistic effect may be obtained. is there.
  • biocidal active ingredients examples include 2,4,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluoroisophthalonitrile, 5-chloro-2,4-difluoro- Isophthalonitrile compounds such as 6-methoxyisophthalonitrile; pyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine; pyrithione compounds such as zinc pyrithione, sodium pyrithione and copper pyrithione Benzimidazole compounds such as methyl benzimidazol-2-ylcarbamate, methyl 1-butylcarbamoylbenzimidazol-2-ylcarbamate, 2- (thiazol-4-yl) benzimidazole; carbamates such as zinc dimethyldithiocarbamate Compounds: Imazaril, Tebucona Azole compounds such as benzene, hexaconazole and
  • the bactericidal effect of the chemical solution was evaluated by the following test.
  • Pseudomonas aeruginosa Pseudomonas aeruginosa NBRC13275 strain
  • a nutrient broth ordinary bouillon “Eiken” manufactured by Eiken Chemical Co., Ltd.
  • the obtained culture solution was diluted 100 times with a fresh nutrient broth liquid medium to obtain a bacterial solution.
  • Each 40 ⁇ L of the drug solution to be tested was dropped on a 96-well microplate.
  • Each 60 ⁇ L of the bacterial solution was added to the chemical solution.
  • the microplate was allowed to stand in the dark at 31 ° C. for 24 hours and cultured.
  • the presence or absence of bacterial growth was examined with the naked eye. A group in which no growth was observed was determined as a group in which growth inhibition was observed.
  • Example 2-Methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI, manufactured by Nippon Soda Co., Ltd.) was dissolved in dimethyl sulfoxide to obtain an MTI solution.
  • MTI Methyl-4,5-trimethylene-4-isothiazolin-3-one
  • HHT Hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine
  • HHT triazine preservative “Bestside-1087T” manufactured by Nippon Soda Co., Ltd.
  • 2-Bromo-2-nitropropane-1,3-diol (BNPD, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in dimethyl sulfoxide to obtain a BNPD solution.
  • DBNE 2,2-Dibromo-2-nitroethanol
  • DBNE-75P 2,2-Dibromo-3-nitrilopropionamide
  • DBNPA didecyldimethylammonium chloride
  • DDAC didecyldimethylammonium chloride
  • Benzalkonium chloride (BEC, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in dimethyl sulfoxide to obtain a BEC solution.
  • Zinc pyrithione (ZPT, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in dimethyl sulfoxide to obtain a ZPT solution.
  • Polyhexamethylene guanidine hydrochloride (PHMG, Nippon Soda Co., Ltd.) was dissolved in purified water to obtain a PHMG solution.
  • Polyhexamethylene biguanide hydrochloride (PHMB, Nippon Soda Co., Ltd.) was dissolved in purified water to obtain a PHMB solution.
  • MIC with MTI alone is 50 ppm
  • MIC with HHT alone is 200 ppm
  • MIC with BNPD alone is 6.25 ppm
  • MIC with DBNE alone is 6.25 ppm
  • MIC with DBNPA alone is 12.5 ppm
  • DDAC alone The MIC was 12.5 ppm
  • the MIC with BEC alone was 50 ppm
  • the MIC with ZPT alone was 25 ppm
  • the MIC with PHMG alone was 12.5 ppm
  • the MIC with PHMB alone was 12.5 ppm.
  • the FIC index (Fractional Inhibitory Concentration index) was calculated by the following formula.
  • FIC index a / a0 + b / b0 a0: MIC with component A alone b0: MIC with component B alone a: MIC of A component when A component and B component are used together b: MIC of B component when A component and B component are used together
  • the FIC index represents the effect of the combined use of the A component and the B component. When the FIC index is 1, it indicates that there is an additive effect by the combined use of the A component and the B component. When the FIC index is greater than 1, it indicates that there is an antagonistic effect by the combined use of the A component and the B component. When the FIC index is less than 1, it indicates that the combination of the A component and the B component has a synergistic effect. Tables 10 to 18 show MICs when MTI is used in combination with other drugs.
  • the fungicide composition of the present invention comprises MTI, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione,
  • the bactericidal property is improved with a synergistic action by the combined use with polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, or a compound represented by the formula (1).
  • the bactericidal composition of the present invention has a sufficient bactericidal effect.
  • a disinfectant composition can be provided.

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Abstract

A disinfectant composition which comprises a component (A): 2-methyl-4,5-trimethylene-4-isothiazoline-3-on, and a component (B): at least one selected from the group consisting of a compound represented by formula (1), hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione, polyhexamethylene guanidine hydrochloride, and polyhexamethylene biguanide hydrochloride. (In formula (1), X1 and X2 are each independently a bromo group, a nitro group, or a cyano group, provided that at least one of X1 and X2 is a bromo group. R1 is a methyl group, a hydroxymethyl group, or a bromo group. R2 is a methyl group, a hydroxymethyl group, or an aminocarbonyl group.)

Description

殺菌剤組成物Disinfectant composition
　本発明は、殺菌剤組成物に関する。より詳細に、本発明は、細菌、かび、酵母、藻などの防除に用いられる殺菌剤組成物に関する。
　本願は、２０１３年１２月２０日に、日本に出願された特願２０１３－２６３７０７号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a fungicide composition. More specifically, the present invention relates to a fungicide composition used for controlling bacteria, molds, yeasts, algae and the like.
This application claims priority based on Japanese Patent Application No. 2013-263707 for which it applied to Japan on December 20, 2013, and uses the content here.
　４－イソチアゾリン－３－オン骨格を有する殺微生物性化合物は、イソチアゾリン系殺菌剤と総称され、細菌、かび、酵母、藻等の有害微生物の防除に利用されている。イソチアゾリン系殺菌剤の代表例として、２－メチル－４－イソチアゾリン－３－オン（以下Ｈ－ＭＩＴと略称することがある。）、５－クロロ－２－メチル－４－イソチアゾリン－３－オン（以下Ｃｌ－ＭＩＴと略称することがある。）、１，２－ベンズイソチアゾリン－３－オン（以下ＢＩＴと略称することがある。）、２－ｎ－オクチル－４－イソチアゾリン－３－オン、４，５－ジクロロ－２－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、２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン（以下ＭＴＩと略称することがある。）等が挙げられる。 Microbicidal compounds having a 4-isothiazolin-3-one skeleton are collectively referred to as isothiazoline fungicides and are used to control harmful microorganisms such as bacteria, fungi, yeasts and algae. Representative examples of isothiazoline fungicides include 2-methyl-4-isothiazolin-3-one (hereinafter sometimes abbreviated as H-MIT), 5-chloro-2-methyl-4-isothiazolin-3-one ( Hereinafter abbreviated as Cl-MIT), 1,2-benzisothiazolin-3-one (hereinafter sometimes abbreviated as BIT), 2-n-octyl-4-isothiazolin-3-one, 4 , 5-dichloro-2-octyl-4-isothiazolin-3-one, 2-n-butyl-1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazoline-3- ON (hereinafter sometimes abbreviated as MTI) and the like.
　ところで、活性成分の安定性を高めたり、防除できる菌の範囲を広げたりするために、複数種の活性成分を組み合わせることが試みられている。
　例えば、特許文献１は２－メチル－４－イソチアゾリン－３－オンと２－ブロモ－２－ニトロ－１，３－プロパンジオールとの組み合わせからなるものを提案している。特許文献２は５－クロロ－２－メチル－４－イソチアゾリン－３－オンと２－ブロモ－２－ニトロ－１，３－プロパンジオールとの組み合わせからなるものを提案している。特許文献３はヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－ｓ－トリアジン等の抗菌性Ｎ－ホルマールと２－ｎ－オクチル－４－イソチアゾリン－３－オン等の殺菌剤との組み合わせからなるものを提案している。 By the way, in order to increase the stability of active ingredients or to expand the range of bacteria that can be controlled, attempts have been made to combine plural kinds of active ingredients.
For example, Patent Document 1 proposes a combination of 2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitro-1,3-propanediol. Patent Document 2 proposes a combination of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitro-1,3-propanediol. Patent Document 3 describes an antibacterial N-formal such as hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine and a bactericide such as 2-n-octyl-4-isothiazolin-3-one. Proposes a combination.
特開平０４－００９３０５号公報Japanese Unexamined Patent Publication No. 04-009305 特開平０７－０３３６１４号公報Japanese Patent Laid-Open No. 07-033614 特表２００３－５１５６１４号公報Special table 2003-515614
　本発明の目的は、２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンを用いた、新たな殺菌剤組成物を提供することである。 An object of the present invention is to provide a new fungicide composition using 2-methyl-4,5-trimethylene-4-isothiazolin-3-one.
　上記目的を達成するために鋭意研究した結果、以下の態様を包含する本発明を完成するに至った。
〔1〕　成分（A）：２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと、
　成分（B）：式（1）で表される化合物、ヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－ｓ－トリアジン、ジデシルジメチルアンモニウムクロライド、塩化ベンザルコニウム、ジンクピリチオン、ポリヘキサメチレングアニジン塩酸塩、およびポリヘキサメチレンビグアナイド塩酸塩からなる群から選ばれる少なくとも１つと
を含有する、殺菌剤組成物。 As a result of earnest research to achieve the above object, the present invention including the following aspects has been completed.
[1] Component (A): 2-methyl-4,5-trimethylene-4-isothiazolin-3-one,
Component (B): compound represented by formula (1), hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione, polyhexa A disinfectant composition comprising methyleneguanidine hydrochloride and at least one selected from the group consisting of polyhexamethylene biguanide hydrochloride.
Figure JPOXMLDOC01-appb-C000002
 （式（1）中、Ｘ1およびＸ2はそれぞれ独立にブロモ基、ニトロ基またはシアノ基を示す。ただし、Ｘ1およびＸ2のいずれか少なくとも１つはブロモ基である。Ｒ1はメチル基、ヒドロキシメチル基またはブロモ基を示す。Ｒ2はメチル基、ヒドロキシメチル基またはアミノカルボニル基を示す。）
Figure JPOXMLDOC01-appb-C000002
 (In the formula (1), X 1 and X 2 each independently represent a bromo group, a nitro group or a cyano group, provided that at least one of X 1 and X 2 is a bromo group. R 1 is methyl. And R 2 represents a methyl group, a hydroxymethyl group or an aminocarbonyl group.)
〔２〕　式（1）で表される化合物が、２－ブロモ－２－ニトロプロパン－１，３－ジオール、２，２－ジブロモ－２－ニトロエタノール、または２，２－ジブロモ－３－ニトリロプロピオンアミドである、〔１〕に記載の殺菌剤組成物。
〔３〕　成分（B）の量は、成分（A）１００質量部に対して１～１００００質量部である、〔１〕に記載の殺菌剤組成物。
〔４〕　成分（B）が、ヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－ｓ－トリアジン、２－ブロモ－２－ニトロプロパン－１，３－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、ジデシルジメチルアンモニウムクロライド、塩化ベンザルコニウム、ジンクピリチオン、ポリヘキサメチレングアニジン塩酸塩、またはポリヘキサメチレンビグアナイド塩酸塩である、〔３〕に記載の殺菌剤組成物。 [2] The compound represented by the formula (1) is 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, or 2,2-dibromo-3-nitrilo The fungicidal composition according to [1], which is propionamide.
[3] The fungicide composition according to [1], wherein the amount of the component (B) is 1 to 10,000 parts by mass with respect to 100 parts by mass of the component (A).
[4] Component (B) is hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo- 2-nitroethanol, 2,2-dibromo-3-nitrilopropionamide, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione, polyhexamethyleneguanidine hydrochloride, or polyhexamethylenebiguanide hydrochloride [3] The disinfectant composition described in 1.
　本発明によれば、複数の殺菌剤を用いることで、単一成分を使い続けることによる耐性菌の出現の可能性を低下させることができ、さらに優れた殺菌効果を有する、新たな殺菌剤組成物が提供される。 According to the present invention, by using a plurality of bactericides, it is possible to reduce the possibility of emergence of resistant bacteria by continuing to use a single component, and a new bactericidal composition having a further excellent bactericidal effect Things are provided.
　以下、本発明の好ましい例を説明するが、本発明はこれら例に限定されることはない。本発明の趣旨を逸脱しない範囲で、構成の付加、省略、置換、およびその他の変更が可能である。
　本発明の殺菌剤組成物は、成分（A）：２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと、　成分（B）：式（1）で表される化合物、ヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－ｓ－トリアジン、ジデシルジメチルアンモニウムクロライド、塩化ベンザルコニウム、ジンクピリチオン、ポリヘキサメチレングアニジン塩酸塩、およびポリヘキサメチレンビグアナイド塩酸塩からなる群から選ばれる少なくとも１つとを含有する。 Hereinafter, preferred examples of the present invention will be described, but the present invention is not limited to these examples. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit of the present invention.
The fungicide composition of the present invention comprises component (A): 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, component (B): a compound represented by formula (1), hexahydro- Selected from the group consisting of 1,3,5-tris (2-hydroxyethyl) -s-triazine, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione, polyhexamethylene guanidine hydrochloride, and polyhexamethylene biguanide hydrochloride And at least one of the above.
Figure JPOXMLDOC01-appb-C000003
 （式（1）中、Ｘ1およびＸ2はそれぞれ独立にブロモ基、ニトロ基またはシアノ基を示す。ただし、Ｘ1およびＸ2のいずれか少なくとも１つはブロモ基である。Ｒ1はメチル基、ヒドロキシメチル基またはブロモ基を示す。Ｒ2はメチル基、ヒドロキシメチル基またはアミノカルボニル基を示す。）
Figure JPOXMLDOC01-appb-C000003
 (In the formula (1), X 1 and X 2 each independently represent a bromo group, a nitro group or a cyano group, provided that at least one of X 1 and X 2 is a bromo group. R 1 is methyl. And R 2 represents a methyl group, a hydroxymethyl group or an aminocarbonyl group.)
　成分（A）である２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンは、式（2）で表わされる化合物である。 Component (A) 2-methyl-4,5-trimethylene-4-isothiazolin-3-one is a compound represented by the formula (2).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　成分（B）のひとつであるヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－ｓ－トリアジンは式（3）で表わされる化合物である。 One of the components (B), hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, is a compound represented by the formula (3).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　成分（B）のひとつであるジデシルジメチルアンモニウムクロライドは式（4）で表わされる化合物である。 Didecyldimethylammonium chloride, which is one of the components (B), is a compound represented by the formula (4).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　成分（B）のひとつである塩化ベンザルコニウムは式（5）で表わされる化合物である。 Benzalkonium chloride, which is one of the components (B), is a compound represented by the formula (5).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　成分（B）のひとつであるジンクピリチオンは式（6）で表わされる化合物である。 Zinc pyrithione, which is one of the components (B), is a compound represented by the formula (6).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　成分（B）のひとつであるポリヘキサメチレングアニジン塩酸塩は式（7）で表わされる化合物である。 Polyhexamethylene guanidine hydrochloride, which is one of the components (B), is a compound represented by the formula (7).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　成分（B）のひとつであるポリヘキサメチレンビグアナイド塩酸塩は式（8）で表わされる化合物である。 Polyhexamethylene biguanide hydrochloride, which is one of the components (B), is a compound represented by the formula (8).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　成分（B）のひとつである式（1）で表される化合物としては、２－ブロモ－２－ニトロプロパン－１，３－ジオール、２，２－ジブロモ－２－ニトロエタノール、または２，２－ジブロモ－３－ニトリロプロピオンアミドが好ましい。
　２－ブロモ－２－ニトロプロパン－１，３－ジオールは、式（1a）で表わされる化合物であり、２，２－ジブロモ－２－ニトロエタノールは、式（1b）で表わされる化合物であり、２，２－ジブロモ－３－ニトリロプロピオンアミドは、式（1c）で表わされる化合物である。
　これら成分（B）は、１種単独でまたは２種類以上を組み合わせて用いることができる。 Examples of the compound represented by the formula (1) which is one of the components (B) include 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, and 2,2 -Dibromo-3-nitrilopropionamide is preferred.
2-bromo-2-nitropropane-1,3-diol is a compound represented by the formula (1a), and 2,2-dibromo-2-nitroethanol is a compound represented by the formula (1b); 2,2-Dibromo-3-nitrilopropionamide is a compound represented by the formula (1c).
These components (B) can be used alone or in combination of two or more.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　本発明の殺菌剤組成物における、成分（B）の量は、成分（A）に対して、特に限定されるものではなく、対象となる菌によっても異なる場合もあるが、成分（A）１００質量部に対して、好ましくは１～１００００質量部であり、より好ましくは２～９００質量部である。 The amount of component (B) in the fungicide composition of the present invention is not particularly limited with respect to component (A), and may vary depending on the target fungus, but component (A) 100 The amount is preferably 1 to 10,000 parts by mass, more preferably 2 to 900 parts by mass with respect to parts by mass.
　成分（B）が式（1）で表される化合物からなる群から選ばれる少なくとも１つであるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは１０～１５０質量部である。
　成分（B）がヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－ｓ－トリアジンであるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは１５０～９００質量部である。
　成分（B）が、ジデシルジメチルアンモニウムクロライドおよび塩化ベンザルコニウムからなる群から選ばれる少なくとも１つであるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは２０～５００質量部である。
　成分（B）が、ポリヘキサメチレングアニジン塩酸塩およびポリヘキサメチレンビグアナイド塩酸塩からなる群から選ばれる少なくとも１つであるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは２～３００質量部である。
　成分（Ｂ）がジンクピリチオンであるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは５～１５０質量部である。 When the component (B) is at least one selected from the group consisting of compounds represented by the formula (1), the amount of the component (B) is preferably 10 150 parts by mass.
When component (B) is hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, the amount of component (B) is preferably 150 with respect to 100 parts by mass of component (A). ~ 900 parts by mass.
When component (B) is at least one selected from the group consisting of didecyldimethylammonium chloride and benzalkonium chloride, the amount of component (B) is preferably based on 100 parts by mass of component (A) 20 to 500 parts by mass.
When component (B) is at least one selected from the group consisting of polyhexamethylene guanidine hydrochloride and polyhexamethylene biguanide hydrochloride, the amount of component (B) is based on 100 parts by mass of component (A) The amount is preferably 2 to 300 parts by mass.
When component (B) is zinc pyrithione, the amount of component (B) is preferably 5 to 150 parts by mass with respect to 100 parts by mass of component (A).
　成分（B）が、２－ブロモ－２－ニトロプロパン－１，３－ジオールであるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは２０～３０質量部である。
　成分（B）が、２，２－ジブロモ－２－ニトロエタノールであるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは２０～８０質量部である。
　成分（B）が、２，２－ジブロモ－３－ニトリロプロピオンアミドであるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは１０～１５０質量部である。
　成分（B）が、ジデシルジメチルアンモニウムクロライドであるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは３０～８０質量部である。
　成分（B）が、塩化ベンザルコニウムであるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは２０～５００質量部である。
　成分（B）が、ポリヘキサメチレングアニジン塩酸塩であるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは２～３００質量部である。
　成分（B）が、ポリヘキサメチレンビグアナイド塩酸塩であるとき、成分（B）の量は、成分（A）１００質量部に対して、好ましくは３～１５０質量部である。 When component (B) is 2-bromo-2-nitropropane-1,3-diol, the amount of component (B) is preferably 20 to 30 parts by mass with respect to 100 parts by mass of component (A). It is.
When component (B) is 2,2-dibromo-2-nitroethanol, the amount of component (B) is preferably 20 to 80 parts by mass with respect to 100 parts by mass of component (A).
When component (B) is 2,2-dibromo-3-nitrilopropionamide, the amount of component (B) is preferably 10 to 150 parts by mass with respect to 100 parts by mass of component (A).
When component (B) is didecyldimethylammonium chloride, the amount of component (B) is preferably 30 to 80 parts by mass with respect to 100 parts by mass of component (A).
When the component (B) is benzalkonium chloride, the amount of the component (B) is preferably 20 to 500 parts by mass with respect to 100 parts by mass of the component (A).
When component (B) is polyhexamethylene guanidine hydrochloride, the amount of component (B) is preferably 2 to 300 parts by mass with respect to 100 parts by mass of component (A).
When component (B) is polyhexamethylene biguanide hydrochloride, the amount of component (B) is preferably 3 to 150 parts by mass with respect to 100 parts by mass of component (A).
　本発明の殺菌剤組成物の剤形は特に限定されないが、室温において液状であることが好ましい。液状殺菌剤組成物として具体的には、水溶剤、懸濁剤、乳剤、エマルション、サスポエマルション等が挙げられる。これらの剤形は、含有される殺菌成分の物性や殺菌剤組成物の用途に応じて選択することができる。 The dosage form of the fungicide composition of the present invention is not particularly limited, but is preferably liquid at room temperature. Specific examples of the liquid disinfectant composition include an aqueous solvent, a suspending agent, an emulsion, an emulsion, and a suspoemulsion. These dosage forms can be selected according to the physical properties of the sterilizing component contained and the application of the sterilizing composition.
　本発明の殺菌剤組成物には、必要に応じて、溶媒、界面活性剤等の成分が含まれていてもよい。 The fungicide composition of the present invention may contain components such as a solvent and a surfactant as necessary.
　本発明の殺菌剤組成物に含有することのできる溶媒としては、水または有機溶剤がある。有機溶剤としては、トルエン、キシレン、メチルナフタレンなどの非極性溶剤；エタノール、イソプロパノールなどの低級アルコール；エチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、グリセリンなどのグリコール系溶剤；アセトン、メチルエチルケトン、シクロヘキサノンなどのケトン系溶剤；ジメチルホルムアミド、プロピレンカーボネート、ジメチルスルホキシド、アセトニトリル、Ｎ－メチルピロリドンなどの極性溶剤などが挙げられる。 The solvent that can be contained in the bactericide composition of the present invention is water or an organic solvent. Organic solvents include nonpolar solvents such as toluene, xylene, and methylnaphthalene; lower alcohols such as ethanol and isopropanol; glycol solvents such as ethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and glycerin; acetone, methyl ethyl ketone, and cyclohexanone Ketone solvents such as dimethylformamide, propylene carbonate, dimethyl sulfoxide, acetonitrile, and polar solvents such as N-methylpyrrolidone.
　本発明の殺菌剤組成物に含有することのできる界面活性剤としては、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルベンジルジメチルアンモニウム塩、アルキルピリジニウム塩、ポリヘキサメチレンビグアナイドなどのカチオン性界面活性剤；アルキルベンゼンスルホン酸塩、アルキル硫酸塩、アルキルナフタレンスルホン酸塩、ジアルキルスルホコハク酸塩、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エーテルカルボン酸塩、ポリオキシエチレンスチレン化フェニルエーテルサルフェートアンモニウム塩、リグニンスルホン酸塩、高級脂肪酸塩、α－オレフィン脂肪酸塩、α－スルホ脂肪酸塩などのアニオン性界面活性剤；　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フェニルエーテル、ポリオキシアルキレン脂肪酸エステル、ポリオキシアルキレンヒマシ油、ショ糖脂肪酸エステル、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などのノニオン系界面活性剤；　アルキルメチルアミンオキシド、アルキルカルボキシベタイン、アルキルスルホベタインなどの両性界面活性剤が挙げられる。 Examples of the surfactant that can be contained in the fungicide composition of the present invention include cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylbenzyldimethylammonium salt, alkylpyridinium salt, and polyhexamethylene biguanide. Alkylbenzene sulfonate, alkyl sulfate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether carboxylate, polyoxyethylene styrenated phenyl ether sulfate ammonium salt, lignin Anionic surfactants such as sulfonate, higher fatty acid salt, α-olefin fatty acid salt, α-sulfo fatty acid salt; polyoxyalkylene arylphenyl ester Nonionic surfactants such as ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene castor oil, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester; alkylmethylamine oxide, alkyl Examples include amphoteric surfactants such as carboxybetaine and alkylsulfobetaine.
　本発明の殺菌剤組成物には、成分（A）および成分（B）以外に、他の殺生物活性成分が含有されていてもよい。前記殺生物活性成分としては、殺微生物性、防腐性、防カビ性、防藻性、防蟻性、殺虫性などの活性を有するものが挙げられる。このような殺生物活性成分を含有することにより、本発明の殺菌剤組成物は、防除対象の範囲が広がるとともに、長期間の保存が可能になり、あるいは更なる相乗効果が得られる可能性がある。 In addition to the component (A) and the component (B), the biocidal composition of the present invention may contain other biocidal active ingredients. Examples of the biocidal active ingredient include those having activities such as microbicidal properties, antiseptic properties, fungicidal properties, algal-proofing properties, ant-proofing properties, and insecticidal properties. By containing such a biocidal active ingredient, the fungicide composition of the present invention has a wide range of control targets and can be stored for a long period of time, or a further synergistic effect may be obtained. is there.
　殺生物活性成分としては、例えば、２，４，５，６－テトラクロロイソフタロニトリル、５－クロロ－２，４，６－トリフロオロイソフタロニトリル、５－クロロ－２，４－ジフロオロ－６－メトキシイソフタロニトリル等のイソフタロニトリル系化合物；２，３，５，６－テトラクロロ－４－（メチルスルホニル）ピリジン等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、銅ピリチオン等のピリチオン系化合物；ベンズイミダゾール－２－イルカルバミン酸メチル、１－ブチルカルバモイルベンズイミダゾール－２－イルカルバミン酸メチル、２－（チアゾール－４－イル）ベンズイミダゾール等のベンズイミダゾール系化合物；ジンクジメチルジチオカーバメート等のカルバメート系化合物；イマザリル、テブコナゾール、ヘキサコナゾール、エポキシコナゾール等のアゾール系化合物；３－ヨード－２－プロピニル－Ｎ－ブチルカルバメート、ジヨードメチル－ｐ－トリルスルホン、４－クロルフェニル－３－ヨードプロパルギルホルマール等のヨード系化合物；２－（４－チオシアノメチルチオ）ベンゾチアゾール、メチレンビスチオシアネート等のチオシアネート系化合物；ドデシルグアニジン塩酸塩、ドデシルグアニジン酢酸塩、イミノクタジン酢酸塩等のグアニジン系化合物；塩化セチルピリジウム、塩化ベンザルコニウム、塩化ベンゼトニウム、塩化デカリニウム、ジデシルジメチルアンモニウムクロライド等の４級アンモニウム塩化合物；３－（３，４－ジクロロフェニル）－１，１－ジメチルウレア等のフェニルウレア系化合物；２－メチルチオ－４－ｔ－ブチルアミノ－６－シクロプロピルアミノ－Ｓ－トリアジン等のトリアジン系化合物；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、ビフェントリンなどのピレスロイド系化合物；イミダクロプリド、アセタミプリドなどのネオニコチノイド系化合物；フェニトロチオン、ホキシム、ピリダフェンチオンなどの有機リン系化合物；などが挙げられる。 Examples of biocidal active ingredients include 2,4,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluoroisophthalonitrile, 5-chloro-2,4-difluoro- Isophthalonitrile compounds such as 6-methoxyisophthalonitrile; pyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine; pyrithione compounds such as zinc pyrithione, sodium pyrithione and copper pyrithione Benzimidazole compounds such as methyl benzimidazol-2-ylcarbamate, methyl 1-butylcarbamoylbenzimidazol-2-ylcarbamate, 2- (thiazol-4-yl) benzimidazole; carbamates such as zinc dimethyldithiocarbamate Compounds: Imazaril, Tebucona Azole compounds such as benzene, hexaconazole and epoxiconazole; iodine compounds such as 3-iodo-2-propynyl-N-butylcarbamate, diiodomethyl-p-tolylsulfone, 4-chlorophenyl-3-iodopropargyl formal Compound: Thiocyanate compounds such as 2- (4-thiocyanomethylthio) benzothiazole and methylenebisthiocyanate; Guanidine compounds such as dodecylguanidine hydrochloride, dodecylguanidine acetate, iminoctazine acetate; cetylpyridinium chloride, benzalkco chloride Quaternary ammonium salt compounds such as nium, benzethonium chloride, decalinium chloride, and didecyldimethylammonium chloride; phenylurea compounds such as 3- (3,4-dichlorophenyl) -1,1-dimethylurea; Triazine compounds such as luthio-4-t-butylamino-6-cyclopropylamino-S-triazine; pyrethroid compounds such as cyfluthrin, cypermethrin, deltamethrin, fenpropatoline, bifenthrin; neonicotinoids such as imidacloprid and acetamiprid System phosphorus compounds; organophosphorus compounds such as fenitrothion, phoxime, pyridafenthion; and the like.
　以下に実施例を示し、本発明をより詳細に説明する。ただし、本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.
　薬液の殺菌効果を以下の試験で評価した。
（抗微生物活性試験）
　緑膿菌（Pseudomonas aeruginosa NBRC13275株）を、ニュートリエントブロス（栄研化学社製普通ブイヨン「栄研」）液体培地９mＬに植え付けた。これを３１℃の暗所で１８時間振盪培養した。得られた培養液を新鮮なニュートリエントブロス液体培地で１００倍に希釈して、菌液を得た。
　試験対象の薬液を９６穴マイクロプレートに各４０μＬ滴下した。前記菌液を前記薬液に各６０μL滴加した。マイクロプレートを３１℃の暗所に２４時間静置し、培養させた。
　肉眼で菌の増殖の有無を調査した。増殖が認められない区を、増殖抑制が認められた区と判定した。 The bactericidal effect of the chemical solution was evaluated by the following test.
(Antimicrobial activity test)
Pseudomonas aeruginosa (Pseudomonas aeruginosa NBRC13275 strain) was planted in 9 mL of a nutrient broth (ordinary bouillon “Eiken” manufactured by Eiken Chemical Co., Ltd.) liquid medium. This was cultured with shaking in the dark at 31 ° C. for 18 hours. The obtained culture solution was diluted 100 times with a fresh nutrient broth liquid medium to obtain a bacterial solution.
Each 40 μL of the drug solution to be tested was dropped on a 96-well microplate. Each 60 μL of the bacterial solution was added to the chemical solution. The microplate was allowed to stand in the dark at 31 ° C. for 24 hours and cultured.
The presence or absence of bacterial growth was examined with the naked eye. A group in which no growth was observed was determined as a group in which growth inhibition was observed.
実施例
　２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オン（ＭＴＩ、日本曹達社製）をジメチルスルホキシドに溶解させてＭＴＩ溶液を得た。
　ヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－ｓ－トリアジン（ＨＨＴ、日本曹達社製トリアジン系防腐剤「ベストサイド－１０８７Ｔ」）をジメチルスルホキシドに溶解させてＨＨＴ溶液を得た。
　２－ブロモ－２－ニトロプロパン－１，３－ジオール（ＢＮＰＤ、和光純薬工業社製）をジメチルスルホキシドに溶解させてＢＮＰＤ溶液を得た。
　２，２－ジブロモ－２－ニトロエタノール（ＤＢＮＥ、Shanghai SMEC Trading Co., Ltd.製「DBNE-75P」）をジメチルスルホキシドに溶解させてＤＢＮＥ溶液を得た。
　２，２－ジブロモ－３－ニトリロプロピオンアミド（ＤＢＮＰＡ、和光純薬工業社製）をジメチルスルホキシドに溶解させてＤＢＮＰＡ溶液を得た。
　ジデシルジメチルアンモニウムクロライド（ＤＤＡＣ、日本曹達社製）をジメチルスルホキシドに溶解させてＤＤＡＣ溶液を得た。
　塩化ベンザルコニウム（ＢＥＣ、和光純薬工業社製）をジメチルスルホキシドに溶解させてＢＥＣ溶液を得た。
　ジンクピリチオン（ＺＰＴ、和光純薬工業社製）をジメチルスルホキシドに溶解させてＺＰＴ溶液を得た。
　ポリヘキサメチレングアニジン塩酸塩（ＰＨＭＧ、日本曹達社製）を精製水に溶解させてＰＨＭＧ溶液を得た。
　ポリヘキサメチレンビグアナイド塩酸塩（ＰＨＭＢ、日本曹達社製）を精製水に溶解させてＰＨＭＢ溶液を得た。 Example 2-Methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI, manufactured by Nippon Soda Co., Ltd.) was dissolved in dimethyl sulfoxide to obtain an MTI solution.
Hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine (HHT, triazine preservative “Bestside-1087T” manufactured by Nippon Soda Co., Ltd.) was dissolved in dimethyl sulfoxide to obtain an HHT solution.
2-Bromo-2-nitropropane-1,3-diol (BNPD, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in dimethyl sulfoxide to obtain a BNPD solution.
2,2-Dibromo-2-nitroethanol (DBNE, “DBNE-75P” manufactured by Shanghai SMEC Trading Co., Ltd.) was dissolved in dimethyl sulfoxide to obtain a DBNE solution.
2,2-Dibromo-3-nitrilopropionamide (DBNPA, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in dimethyl sulfoxide to obtain a DBNPA solution.
Didecyldimethylammonium chloride (DDAC, Nippon Soda Co., Ltd.) was dissolved in dimethyl sulfoxide to obtain a DDAC solution.
Benzalkonium chloride (BEC, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in dimethyl sulfoxide to obtain a BEC solution.
Zinc pyrithione (ZPT, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in dimethyl sulfoxide to obtain a ZPT solution.
Polyhexamethylene guanidine hydrochloride (PHMG, Nippon Soda Co., Ltd.) was dissolved in purified water to obtain a PHMG solution.
Polyhexamethylene biguanide hydrochloride (PHMB, Nippon Soda Co., Ltd.) was dissolved in purified water to obtain a PHMB solution.
　これらの溶液を、表１～９に示す各化合物の濃度になるように混ぜ合わせ、精製水で希釈して薬液を調製した。各薬液について抗微生物活性試験を行った。その結果を表１～９に示す。表中の「＋」は菌の増殖有り、「－」は菌の増殖無し、「±」は菌の増殖がわずかに認められる場合を、それぞれ示す。 These solutions were mixed so as to have a concentration of each compound shown in Tables 1 to 9, and diluted with purified water to prepare a chemical solution. Each drug solution was tested for antimicrobial activity. The results are shown in Tables 1-9. In the table, “+” indicates the presence of bacterial growth, “−” indicates the absence of bacterial growth, and “±” indicates the case where slight bacterial growth is observed.
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
　表１～９から、各薬液の最小発育阻止濃度（MIC）を求めた。ＭＴＩ単独でのMICは５０ｐｐｍ、ＨＨＴ単独でのMICは２００ｐｐｍ、ＢＮＰＤ単独でのMICは６．２５ｐｐｍ、ＤＢＮＥ単独でのMICは６．２５ｐｐｍ、ＤＢＮＰＡ単独でのMICは１２．５ｐｐｍ、ＤＤＡＣ単独でのMICは１２．５ｐｐｍ、ＢＥＣ単独でのMICは５０ｐｐｍ、ＺＰＴ単独でのMICは２５ｐｐｍ、ＰＨＭＧ単独でのMICは１２．５ｐｐｍ、ＰＨＭＢ単独でのMICは１２．５ｐｐｍであった。 From Tables 1 to 9, the minimum inhibitory concentration (MIC) of each chemical solution was determined. MIC with MTI alone is 50 ppm, MIC with HHT alone is 200 ppm, MIC with BNPD alone is 6.25 ppm, MIC with DBNE alone is 6.25 ppm, MIC with DBNPA alone is 12.5 ppm, DDAC alone The MIC was 12.5 ppm, the MIC with BEC alone was 50 ppm, the MIC with ZPT alone was 25 ppm, the MIC with PHMG alone was 12.5 ppm, and the MIC with PHMB alone was 12.5 ppm.
　次式によってFIC指数（Fractional Inhibitory Concentration index）を算出した。
　FIC指数＝ a / a0 ＋ b / b0
　　a0：A成分単独でのMIC
　　b0：B成分単独でのMIC
　　a：A成分とB成分を併用したときのA成分のMIC
　　b：A成分とB成分を併用したときのB成分のMIC
　FIC指数は、A成分とB成分の併用による効果を表わす。FIC指数が１である場合はA成分とB成分の併用によって相加的作用があることを示す。FIC指数が１より大きい場合はA成分とB成分の併用によって拮抗的作用があることを示す。FIC指数が１より小さい場合はA成分とB成分の併用によって相乗的作用があることを示す。
　ＭＴＩと他の薬剤とを併用したときのMICを表１０～１８に各々示す。 The FIC index (Fractional Inhibitory Concentration index) was calculated by the following formula.
FIC index = a / a0 + b / b0
a0: MIC with component A alone
b0: MIC with component B alone
a: MIC of A component when A component and B component are used together
b: MIC of B component when A component and B component are used together
The FIC index represents the effect of the combined use of the A component and the B component. When the FIC index is 1, it indicates that there is an additive effect by the combined use of the A component and the B component. When the FIC index is greater than 1, it indicates that there is an antagonistic effect by the combined use of the A component and the B component. When the FIC index is less than 1, it indicates that the combination of the A component and the B component has a synergistic effect.
Tables 10 to 18 show MICs when MTI is used in combination with other drugs.
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031
　以上からわかるとおり、本発明の殺菌剤組成物は、ＭＴＩと、ヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－ｓ－トリアジン、ジデシルジメチルアンモニウムクロライド、塩化ベンザルコニウム、ジンクピリチオン、ポリヘキサメチレングアニジン塩酸塩、ポリヘキサメチレンビグアナイド塩酸塩、または式（1）で表される化合物との併用によって相乗的作用を以て殺菌性が改良されている。本発明の殺菌剤組成物は十分な殺菌効果を奏する。 As can be seen from the above, the fungicide composition of the present invention comprises MTI, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione, The bactericidal property is improved with a synergistic action by the combined use with polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, or a compound represented by the formula (1). The bactericidal composition of the present invention has a sufficient bactericidal effect.
　本発明品を用いれば、単一成分を使い続けることによる耐性菌の出現の可能性を低下させることができ、さらに優れた殺菌効果を奏する、細菌、かび、酵母や藻などの防除に用いられる殺菌剤組成物を提供することができる。 If the product of the present invention is used, the possibility of emergence of resistant bacteria by continuing to use a single component can be reduced, and it is used for the control of bacteria, fungi, yeast, algae, etc. that have an excellent bactericidal effect. A disinfectant composition can be provided.

Claims (4)


  1. 　成分（A）：２－メチル－４，５－トリメチレン－４－イソチアゾリン－３－オンと、
    　成分（B）：式（1）で表される化合物、ヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－ｓ－トリアジン、ジデシルジメチルアンモニウムクロライド、塩化ベンザルコニウム、ジンクピリチオン、ポリヘキサメチレングアニジン塩酸塩、およびポリヘキサメチレンビグアナイド塩酸塩からなる群から選ばれる少なくとも１つと
    を含有する、殺菌剤組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式（1）中、Ｘ1およびＸ2はそれぞれ独立にブロモ基、ニトロ基またはシアノ基を示す。ただし、Ｘ1およびＸ2のいずれか少なくとも１つはブロモ基である。Ｒ1はメチル基、ヒドロキシメチル基またはブロモ基を示す。Ｒ2はメチル基、ヒドロキシメチル基またはアミノカルボニル基を示す。）
    Component (A): 2-methyl-4,5-trimethylene-4-isothiazolin-3-one,
    Component (B): compound represented by formula (1), hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione, polyhexa A disinfectant composition comprising methyleneguanidine hydrochloride and at least one selected from the group consisting of polyhexamethylene biguanide hydrochloride.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (1), X 1 and X 2 each independently represent a bromo group, a nitro group or a cyano group, provided that at least one of X 1 and X 2 is a bromo group. R 1 is methyl. And R 2 represents a methyl group, a hydroxymethyl group or an aminocarbonyl group.)
  2. 　式（1）で表される化合物が、２－ブロモ－２－ニトロプロパン－１，３－ジオール、２，２－ジブロモ－２－ニトロエタノール、または２，２－ジブロモ－３－ニトリロプロピオンアミドである、請求項１に記載の殺菌剤組成物。 The compound represented by the formula (1) is 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, or 2,2-dibromo-3-nitrilopropionamide. The disinfectant composition according to claim 1.
  3. 　成分（B）の量は、成分（A）１００質量部に対して１～１００００質量部である、請求項１に記載の殺菌剤組成物。 The fungicide composition according to claim 1, wherein the amount of the component (B) is 1 to 10,000 parts by mass with respect to 100 parts by mass of the component (A).
  4. 　成分（B）が、ヘキサヒドロ－１，３，５－トリス（２－ヒドロキシエチル）－ｓ－トリアジン、２－ブロモ－２－ニトロプロパン－１，３－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、ジデシルジメチルアンモニウムクロライド、塩化ベンザルコニウム、ジンクピリチオン、ポリヘキサメチレングアニジン塩酸塩、またはポリヘキサメチレンビグアナイド塩酸塩である、請求項３に記載の殺菌剤組成物。 Component (B) is hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitro 4. The ethanol according to claim 3, which is ethanol, 2,2-dibromo-3-nitrilopropionamide, didecyldimethylammonium chloride, benzalkonium chloride, zinc pyrithione, polyhexamethylene guanidine hydrochloride, or polyhexamethylene biguanide hydrochloride. Disinfectant composition.
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