JP5457793B2 - Industrial antibacterial agent - Google Patents

Description

  The present invention relates to an industrial antibacterial agent containing flusilazole or a salt thereof.

  Flucilazole (chemical name; methylbis (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane) is a compound represented by the following formula (1), and the compound is effective for agricultural chemicals. A preparation that is used as a component and contains it at a concentration of 39% is known (Non-patent Document 1). It is also known to use an antibacterial composition contained together with other antibacterial compounds for agriculture (Patent Document 1).

JP-A-7-101183

Safety Data Sheet (SAFETY DATA SHEET), “NUSTAR 40EC”, Du Pont de Nemours (France) A. S. URL: http://www2.dupont.com/Crop_Protection/en_DZ/assets/downloads/pdfs/msds/PUNCH40EC.pdf

  On the other hand, development of antibacterial agents that can be used in a wide range of industrial applications and have good antibacterial activity in each of these applications is expected.

  As a result of intensive studies to solve the above problems, the present inventor has found that when an antibacterial composition containing flusilazole or a salt thereof is applied for industrial use, it has good antibacterial activity against various molds. Furthermore, by using together with a specific antibacterial compound, it has been found that an antibacterial spectrum is broadened and a synergistic increase in antibacterial activity is observed, and the present invention has been completed.

That is, the present invention relates to the following [1] to [10].
[1] An industrial antibacterial agent containing flusilazole or a salt thereof.
[2] Further, an isothiazoline compound represented by formula (2), a benzisothiazoline compound represented by formula (3), a haloacetylene compound represented by formula (4), and a carbamoylimidazole compound represented by formula (5) Selected from the group consisting of a compound, an alkoxyalkylamine compound represented by formula (6), a tetrahydrothiophene dioxide compound represented by formula (7), a quinolone compound represented by formula (8), and salts thereof. The industrial antibacterial agent according to the above [1], containing one or more kinds.

[Wherein, R ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. Show. ]

[Wherein, ring A ₁ represents an optionally substituted benzene ring, and Y represents a hydrogen atom or an optionally substituted hydrocarbon group. ]

[Wherein, X represents a halogen atom, R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an optionally substituted hydrocarbon group, and m represents an integer of 0 or 1. ]

[Wherein, R ₇ and R ₈ are the same or different and each represents a hydrogen atom or an optionally substituted hydrocarbon group, and n represents an integer of 1 to 6. ]

[Wherein, R ₉ represents an alkyl group substituted with one or more alkoxy groups, and R ₁₀ and R ₁₁ are the same or different and each represents hydrogen or an alkyl group. ]

[Wherein Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same or different and each represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. ]

[Wherein, A ₃ ring represents an optionally substituted 6-membered aromatic ring, and R ₁₂ represents a hydrogen atom or an optionally substituted hydrocarbon group. ]

[3] The isothiazoline-based compound is 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazoline-3- ON, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one and 4,5-dichloro-2-n-octyl-4- The industrial antibacterial agent according to [2] above, which is one or more selected from the group consisting of isothiazoline-3-one.
[4] The isothiazoline-based compound is selected from 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-n-octyl-4-isothiazolin-3-one The industrial antibacterial agent according to the above [2], which is one or more selected from the group consisting of:
[5] The above-mentioned [2], wherein the benzisothiazoline compound is one or two selected from 1,2-benzisothiazolin-3-one and Nn-butyl-1,2-benzisothiazolin-3-one. ] The industrial antibacterial agent as described in.
[6] The industrial antibacterial agent according to the above [2], wherein the haloacetylene compound is 3-iodo-2-propynyl N-butyl carbamate.
[7] The industrial product according to [2], wherein the carbamoylimidazole compound is N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] -1H-imidazole-1-carboxamide. Antibacterial agent.
[8] The industrial antibacterial agent according to [2], wherein the alkoxyalkylamine compound is 3-dodecyloxypropylamine or a salt thereof.
[9] The industrial antibacterial agent according to [2], wherein the tetrahydrothiophene dioxide-based compound is 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide.
[10] The above [2], wherein the quinolone compound is 5-ethyl-5,8-dihydro-8-oxo-1,3-dioxolo [4,5-g] quinoline-7-carboxylic acid or a salt thereof. The industrial antibacterial agent described in 1.

  According to the present invention, an industrial antibacterial agent containing flusilazole or a salt thereof having antibacterial activity against various molds can be obtained. In addition, by using a specific antibacterial compound in combination, the antibacterial spectrum is expanded and the antibacterial activity is synergistically increased, so that it can be used in various modes and can be used for a wide range of industrial applications. Antibacterial agent can be obtained.

  The flusilazole used in the present invention may be in the form of a salt. Examples of the salt include salts with mineral acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid; formic acid, acetic acid, trifluoroacetic acid, phthalate Examples include salts with organic acids such as acid, fumaric acid, oxalic acid, tartaric acid, maleic acid, citric acid, succinic acid, malic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

  As flusilazole or a salt thereof used in the present invention, a commercially available product may be used, or a product manufactured according to a known technique may be used, but it is convenient to use a commercially available product.

  The industrial antibacterial agent of the present invention includes isothiazoline compounds, benzisothiazoline compounds, haloacetylene compounds, carbamoylimidazole compounds, alkoxyalkylamine compounds, tetrahydrothiophene dioxide compounds, in addition to the above-mentioned flusilazole or a salt thereof One or two or more antibacterial compounds selected from the group consisting of quinolone compounds and salts thereof may be used in combination. By using the antibacterial compound in combination, the antibacterial spectrum is expanded and the antibacterial activity is synergistically increased.

  The isothiazoline-based compound is represented by the following formula (2).

[Wherein, R ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. Show. ]

In the formula (2), the hydrocarbon group of the “optionally substituted hydrocarbon group” represented by R ₁ is preferably a hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon group having 1 to 14 carbon atoms. Are more preferable, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group.

  Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 1-methylbutyl, 1-ethylpropyl, 1,1- Dimethylpropyl, 2,2-dimethylpentyl, n-hexyl, isohexyl, 2-ethylbutyl, n-heptyl, isoheptyl, n-octyl, isooctyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1,1- Examples thereof include alkyl groups having 1 to 10 carbon atoms such as dimethylhexyl, 1-ethyl-1-methylpentyl, 1,1-diethylbutyl, 2-ethylhexyl, nonyl and decyl, and preferably alkyl groups having 1 to 8 carbon atoms. .

  Examples of the alkenyl group include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 1-pentenyl, Examples thereof include alkenyl groups having 2 to 6 carbon atoms such as 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and 5-hexenyl.

  Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, Examples thereof include alkynyl groups having 2 to 6 carbon atoms such as 2-hexynyl, 3-hexynyl, 4-hexynyl and 5-hexynyl.

  Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.

  Examples of the aryl group include aryl groups having 6 to 14 carbon atoms such as phenyl, naphthyl, anthracenyl, phenanthrenyl and the like.

Examples of the substituent of the “optionally substituted hydrocarbon group” represented by R ₁ include hydroxyl group; halogen atom of chlorine, fluorine, bromine and iodine; cyano group; amino group; carboxyl group; methoxy, ethoxy, propoxy, An alkoxy group having 1 to 4 carbon atoms such as butoxy; an aryloxy group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms such as phenoxy; an alkylthio group having 1 to 4 carbon atoms such as methylthio, ethylthio, propylthio, and butylthio An arylthio group having 6 to 20 carbon atoms such as phenylthio; The substituents may be the same or different, and 1 to 5, preferably 1 to 3 may be substituted.

As the “optionally substituted hydrocarbon group” represented by R ₁ , an unsubstituted hydrocarbon group is preferable, and among them, an alkyl group or a cycloalkyl group is preferable. As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like, and n -8 carbon atoms such as octyl, isooctyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1,1-dimethylhexyl, 1-ethyl-1-methylpentyl, 1,1-diethylbutyl, 2-ethylhexyl Are more preferable, and methyl, ethyl, n-butyl, and n-octyl are more preferable. As the cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and cyclohexyl is more preferable.

R ₁ is preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, methyl, ethyl, propyl, isopropyl, n-butyl, C1-C4 alkyl groups such as isobutyl, sec-butyl, tert-butyl, and n-octyl, isooctyl, sec-octyl (1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, etc.), tert-octyl More preferred are alkyl groups having 8 carbon atoms such as (1,1-dimethylhexyl, 1-ethyl-1-methylpentyl, 1,1-diethylbutyl, etc.), 2-ethylhexyl, and the like, methyl, ethyl, n-butyl, n -Octyl is particularly preferred.

In the formula (2), examples of the halogen atom represented by R ₂ or R ₃ include fluorine, chlorine, bromine and iodine atoms, and among these, a chlorine atom is preferable.

Examples of the “optionally substituted hydrocarbon group” represented by R ₂ or R ₃ include the same as the “optionally substituted hydrocarbon group” represented by R ₁ described above, Among them, an unsubstituted hydrocarbon group is preferable, and an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like is particularly preferable.

R ₂ and R ₃ are the same or different and are each preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom or a chlorine atom.

  Specific examples of the isothiazoline-based compound include 2-methyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro. 2-methyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one, 4-chloro 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazoline-3 -ON etc. are mentioned. Of these, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 5- Chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one and 4,5-dichloro-2-n-octyl-4-isothiazoline-3- On is preferred, with 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-n-octyl-4-isothiazolin-3-one being particularly preferred. The above isothiazoline-based compounds may be used alone or in combination of two or more.

  The benzisothiazoline-based compound is represented by the following formula (3).

[Wherein, ring A ₁ represents an optionally substituted benzene ring, and Y represents a hydrogen atom or an optionally substituted hydrocarbon group. ]

In the formula (3), as the substituent of the “optionally substituted benzene ring” represented by the A ₁ ring, the above-described substituent of the “optionally substituted hydrocarbon group” represented by R ₁ and The same thing can be mentioned, Among these, a C1-C4 alkyl group, such as a halogen atom and methyl, ethyl, propyl, butyl, is preferable. These substituents may be the same or different, and 1 to 4, preferably 1 or 2 may be substituted on the benzene ring. The “optionally substituted benzene ring” represented by A ₁ ring is preferably an unsubstituted benzene ring.

In the formula (3), examples of the “optionally substituted hydrocarbon group” represented by Y include the same as the “optionally substituted hydrocarbon group” represented by R ₁ described above, Among them, an unsubstituted hydrocarbon group is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms (particularly n-butyl) is particularly preferable.

  Y is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (particularly n-butyl).

  Preferable specific examples of the benzisothiazoline-based compound include 1,2-benzisothiazolin-3-one, Nn-butyl-1,2-benzisothiazoline-3-one, and the like. The benzisothiazoline compounds may be used alone or in combination of two or more.

  The haloacetylene compound is represented by the following formula (4).

[Wherein, X represents a halogen atom, R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an optionally substituted hydrocarbon group, and m represents an integer of 0 or 1. ]

  In the formula (4), examples of the halogen atom represented by X include fluorine, chlorine, bromine and iodine atoms, and an iodine atom is particularly preferable.

In the formula (4), the “optionally substituted hydrocarbon group” represented by R ₅ or R ₆ is the same as the “optionally substituted hydrocarbon group” represented by R ₁ described above. Is mentioned. Among them, an unsubstituted hydrocarbon group is preferable, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms is more preferable, an alkyl group having 1 to 10 carbon atoms is further preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. Alkyl groups are even more preferred, and n-butyl is particularly preferred.
One of R ₅ and R ₆ is an optionally substituted hydrocarbon group, the other is preferably a hydrogen atom, one of R ₅ and R ₆ is an alkyl group having 1 to 10 carbon atoms, and the other Is more preferably a hydrogen atom, particularly preferably one of R ₅ and R ₆ is an alkyl group having 1 to 4 carbon atoms (particularly n-butyl) and the other is a hydrogen atom.

  In the formula (4), m represents an integer of 0 or 1, and when m is 0, the haloacetylene compound is an acid amide derivative, and when m is 1, the haloacetylene compound is a carbamate derivative. Of these, carbamate derivatives of haloacetylene compounds in which m is 1 are preferred.

  Specific examples of haloacetylene compounds include 3-chloropropiolic acid amide, N-methyl-3-chloropropiolic acid amide, N-ethyl as acid amide derivatives of haloacetylene compounds when m is 0. -3-chloropropiolic amide, N-propyl-3-chloropropiolic amide, N-butyl-3-chloropropiolic amide, N-hexyl-3-chloropropiolic amide, N-octyl-3 (N-substituted-) 3-chloropropiolic amides such as chloropropiolic amide, N-cyclohexyl-3-chloropropiolic amide; 3-bromopropiolic amide, N-methyl-3-bromopropi All acid amide, N-ethyl-3-bromopropiolic acid amide, N-propyl-3-bromopropiolic acid N-butyl-3-bromopropiolic acid amide, N-hexyl-3-bromopropiolic acid amide, N-octyl-3-bromopropiolic acid amide, N-cyclohexyl-3-bromopropiolic acid amide, etc. (N-substituted-) 3-bromopropiolic amides; 3-iodopropiolic amides, N-methyl-3-iodopropiolic amides, N-ethyl-3-iodopropiolic amides, N-propyl -3-iodopropiolic amide, N-butyl-3-iodopropiolic amide, N-hexyl-3-iodopropiolic amide, N-octyl-3-iodopropiolic amide, N-cyclohexyl-3 -(N-substituted-) 3-iodopropiolic amides such as iodopropiolic amide. Of these, (N-substituted-) 3-iodopropiolic acid amide is preferable, and N-butyl-3-iodopropiolic acid amide is more preferable.

Further, as a carbamate derivative of a haloacetylene compound when m is 1, 3-iodo-2-propynyl N-methylcarbamate, 3-iodo-2-propynyl N-ethylcarbamate, 3-iodo-2-propynyl N -Propyl carbamate, 3-iodo-2-propynyl N-butyl carbamate, 3-iodo-2-propynyl N-hexyl carbamate, 3-iodo-2-propynyl N-octyl carbamate, 3-iodo-2-propynyl N-cyclohexyl Examples include 3-iodo-2-propynyl N-alkyl carbamate such as carbamate, and 3-iodo-2-propynyl N-butyl carbamate is preferable.
The said haloacetylene type compound may be used independently, or may use 2 or more types together.

  The carbamoylimidazole compound is represented by the following formula (5).

[Wherein, R ₇ and R ₈ are the same or different and each represents a hydrogen atom or an optionally substituted hydrocarbon group, and n represents an integer of 1 to 6. ]

In the formula (5), the “optionally substituted hydrocarbon group” represented by R ₇ or R ₈ is the same as the “optionally substituted hydrocarbon group” represented by R ₁ described above. Is mentioned.
R ₇ is preferably an unsubstituted hydrocarbon group, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably n-propyl.
R ₈ is preferably a substituted aryl group, more preferably phenyl substituted with 1 to 3 chlorines, and still more preferably phenyl substituted with 3 chlorines.
n is preferably 2 or 3.

  Preferable specific examples of the carbamoylimidazole compound include N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] -1H-imidazole-1-carboxamide. The carbamoylimidazole compounds may be used alone or in combination of two or more.

  The alkoxyalkylamine compound is represented by the following formula (6).

[Wherein R ₉ represents an alkyl group substituted with one or more alkoxy groups, and R ₁₀ and R ₁₁ are the same or different and each represents a hydrogen atom or an alkyl group. ]

In formula (6), examples of the alkyl group of the “alkyl group substituted with one or more alkoxy groups” represented by R ₉ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- C1-C6 alkyl groups, such as a butyl, a tert- butyl, n-pentyl, n-hexyl, are mentioned, Among these, a C2-C4 alkyl group is preferable. Examples of the alkoxy group substituted on the alkyl group include alkoxy groups having 10 to 20 carbon atoms such as decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, icosyloxy, etc. Sixteen alkoxy groups are preferred, and dodecyloxy is particularly preferred.
Examples of the alkyl group represented by R ₁₀ or R ₁₁ include an alkyl group having 1 to 6 carbon atoms.
R ₁₀ and R ₁₁ are preferably both hydrogen atoms.

  Preferable specific examples of the alkoxyalkylamine compounds include 3-dodecyloxypropylamine. The above alkoxyalkylamine compounds may be used alone or in combination of two or more.

  The tetrahydrothiophene dioxide compound is represented by the following formula (7).

[Wherein Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same or different and each represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. ]

In formula (7), examples of the halogen atom represented by Y ₁ , Y ₂ , Y ₃ or Y ₄ include fluorine, chlorine, bromine and iodine atoms, with a chlorine atom being particularly preferred. In addition, as the “optionally substituted hydrocarbon group” represented by Y ₁ , Y ₂ , Y ₃ or Y ₄ , the “optionally substituted hydrocarbon group” represented by R ₁ described above The same thing is mentioned, Among these, a C1-C4 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, is preferable.

As Y ₁ , Y ₂ , Y ₃ and Y ₄ , all of Y ₁ , Y ₂ , Y ₃ and Y ₄ are halogen atoms, or Y ₁ , Y ₂ and Y ₃ are halogen atoms and Y ₄ is It is preferably a hydrogen atom, or Y ₁ and Y ₄ are halogen atoms and Y ₂ and Y ₃ are preferably hydrogen atoms, and all of Y ₁ , Y ₂ , Y ₃ and Y ₄ are halogen atoms. More preferably, it is particularly preferable that all of Y ₁ , Y ₂ , Y ₃ and Y ₄ are chlorine atoms.

  Specific examples of the tetrahydrothiophene dioxide compound include 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, 3,3,4,4-tetrabromotetrahydrothiophene-1,1-dioxide, 3,4-dichlorotetrahydrothiophene-1,1-dioxide, 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide, 3,3,4-tribromotetrahydrothiophene-1,1-dioxide Of these, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide is particularly preferred. The said tetrahydrothiophene dioxide type compound may be used independently, or may use 2 or more types together.

  The quinolone compound is represented by the following formula (8).

[Wherein, A ₃ ring represents an optionally substituted 6-membered aromatic ring, and R ₁₂ represents a hydrogen atom or an optionally substituted hydrocarbon group. ]

In the above formula (8), examples of the 6-membered aromatic ring of the “optionally substituted 6-membered aromatic ring” represented by A ₃ ring include benzene, pyridine, pyrimidine, pyridazine, pyrazine and the like. Among these, benzene, pyridine and pyrimidine are preferable, and benzene is particularly preferable.

The substituent of the “optionally substituted 6-membered aromatic ring” represented by A ₃ ring is the same as the substituent of the “optionally substituted hydrocarbon group” represented by R ₁ described above. And alkylene dioxy groups having 1 or 2 carbon atoms such as methylenedioxy; cyclic amino groups such as pyrrolidine and piperazine, among them, halogen atoms; alkyl having 1 or 2 carbon atoms such as methylenedioxy Rangeoxy groups; cyclic amino groups such as pyrrolidine and piperazine are preferred. These substituents may be the same or different, 1 to 4 to A ₃ ring, preferably may be one or two substituents.

A ring ₃ is a halogen atom (preferably a fluorine atom); an alkylenedioxy group having 1 or 2 carbon atoms such as methylenedioxy and at least one substituent selected from cyclic amino groups such as pyrrolidine and piperazine. Benzene, pyridine or pyrimidine, each of which may be substituted, is preferred, and benzene substituted with an alkylenedioxy group having 1 or 2 carbon atoms such as methylenedioxy is particularly preferred.

In formula (8), examples of the “optionally substituted hydrocarbon group” represented by R ₁₂ include the same as the “optionally substituted hydrocarbon group” represented by R ₁ described above. Among them, an unsubstituted hydrocarbon group is preferable, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl is more preferable, and ethyl is particularly preferable. .
R ₁₂ is preferably an unsubstituted hydrocarbon group, more preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Is particularly preferred.

  Specific examples of quinolone compounds include 5-ethyl-5,8-dihydro-8-oxo-1,3-dioxolo [4,5-g] quinoline-7-carboxylic acid (generic name: oxolinic acid, The Pesticide). Manual 10th edition (published by British Crop Protection Council), described on page 760), 1-ethyl-7-methyl-4 (1H) -oxo-1,8-naphthyridine-3-carboxylic acid (generic name: nalidixic acid) ), 8-ethyl-5,8-dihydro-5-oxo-2- (1-pyrrolidinyl) pyrido [2,3-d] pyrimidine-6-carboxylic acid (generic name: pyromido acid), 1-ethyl-6 -Fluoro-1,4-dihydro-4-oxo-7- (1-piperazinyl) -1,8-naphthyridine-3-carboxylic acid (generic name: enoxacin), 1-ethyl-4-oxo-6-fluoro- 7- (piperazine -1-yl) -1,4-dihydroquinoline-3-carboxylic acid (generic name: norfloxacin) and the like, among others, 5-ethyl-5,8-dihydro-8-oxo-1,3-dioxolo [ 4,5-g] quinoline-7-carboxylic acid (generic name: oxolinic acid) is preferred. The quinolone compounds may be used alone or in combination of two or more.

  The above-mentioned isothiazoline compounds, benzisothiazoline compounds, haloacetylene compounds, carbamoylimidazole compounds, alkoxyalkylamine compounds, tetrahydrothiophene dioxide compounds, and quinolone compounds are salts with acids in the case of basic compounds. In addition, in the case of an acidic compound, it may be used as a salt with a base.

  Salts with acids include salts with mineral acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid; formic acid, acetic acid, trifluoroacetic acid, phthalic acid, fumaric acid, oxalic acid, tartaric acid, maleic acid, Examples include salts with organic acids such as citric acid, succinic acid, malic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

  As a salt with a base, a salt with an alkali metal such as sodium or potassium; a salt with an alkaline earth metal such as magnesium or calcium; an ammonium salt; a trimethylamine, triethylamine, pyridine, picoline, ethanolamine, diethanolamine or triethanolamine And salts with organic amines such as ethylenediamine, 1,6-hexamethylenediamine, tert-butylamine, cyclohexylamine, benzylamine, dicyclohexylamine, N, N-dibenzylethylenediamine, and the like.

  Isothiazoline compounds, benzisothiazoline compounds, haloacetylene compounds, carbamoylimidazole compounds, alkoxyalkylamine compounds, tetrahydrothiophene dioxide compounds, quinolone compounds, and salts thereof may be commercially available or known. Although what was manufactured according to the technique may be used, it is convenient to use a commercial item.

When antibacterial agents containing flusilazole or a salt thereof are used for agriculture as in the prior art, the concentration of the active ingredient is set high (for example, 39% by weight) in order to be applied to agricultural crops. However, when it is used for industrial purposes as in the present invention, an effect at a low concentration is often required for the active ingredient.
In the industrial antibacterial agent of the present invention, the content of flusilazole or a salt thereof is preferably 0.1% by weight to 30% by weight in order to obtain sufficient antibacterial activity against fungi, and 1% by weight to 30%. Weight percent is more preferred.

  When the above antibacterial compound is used in combination, flusilazole or a salt thereof and the above antibacterial compound (two or more kinds) are used to impart a broader antibacterial spectrum and sufficient antibacterial activity to the industrial antibacterial agent of the present invention. When the above compound is used, the content ratio of the total amount of each compound is preferably 9: 1 to 1: 9 (weight ratio), and 8: 2 to 2: 8 (weight ratio). Particularly preferred. Further, although depending on the dosage form, application object, use environment, etc., the content of flusilazole or a salt thereof is preferably 0.1% by weight to 30% by weight, and more preferably 1% by weight to 30% by weight. The content of the antibacterial compound (the total amount of each compound when two or more are used) is preferably 0.1% by weight to 40% by weight, and more preferably 1% by weight to 40% by weight.

  The industrial antibacterial agent of the present invention is dissolved in a solvent, suspended or dispersed using a surfactant or a dissolution aid, etc., and emulsified as a liquid agent, a suspending agent or a dispersing agent, or by a surfactant. Can be provided as an emulsion. In addition, surfactants and solid carriers can be added to provide wettable powders, flowable powders, powders, and the like.

  Examples of the solvent that can be used in the present invention include water; lower alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1, 3-butanediol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether (methyl carbitol), ethylene glycol monoethyl ether (ethyl carbitol), ethylene glycol monobutyl ether (butyl carbitol), Polyhydric alcohols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; acetone, methyl ethyl ketone, methyl alcohol Ketones such as butyl ketone and propylene carbonate; ethers such as dioxane, tetrahydrofuran and ethyl ether; ethyl acetate, butyl acetate, isobutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate Esters such as dimethyl succinate; aromatic solvents such as benzene, toluene, xylene, methylnaphthalene, dimethylnaphthalene, isopropylnaphthalene, diisopropylnaphthalene, ethylbiphenyl, diethylbiphenyl, solvent naphtha; carbon tetrachloride, chloroform, methylene chloride Halogenated hydrocarbon solvents such as: polar organic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, N-methylpyrrolidone, etc. Can be mentioned. These solvents may be used alone or in combination of two or more. Of these solvents, water, lower alcohols and polyhydric alcohols are preferably used.

  Examples of the surfactant that can be used in the present invention include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethienonyl phenyl ether, polyoxyethylene polyoxypropylene glycol; Examples include anionic surfactants such as ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate esters, lignin sulfonates, and naphthalene sulfonate formalin condensates. . These may be used alone or in combination of two or more.

  Examples of the dissolution aid that can be used in the present invention include carboxylic acids such as capric acid and adipic acid; esters such as diisopropyl adipate, diisopropyl sebacate, isopropyl myristate, and isopropyl palmitate; higher grades such as octyldodecanol and oleyl alcohol. Examples of alcohols include amines such as monoethanolamine and diethanolamine, and these may be used alone or in combination of two or more.

  Examples of solid carriers that can be used in the present invention include minerals such as kaolin clay, attapulgite clay, bentonite, montmorillonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, and natural substances such as corn cob flour and walnut shell flour. Organic substances; synthetic organic substances such as urea; salts such as calcium carbonate and ammonium sulfate; fine powders or granules of synthetic inorganic substances such as synthetic silicon hydroxide.

  The industrial antibacterial agent of the present invention is preferably prepared at 5 to 40 ° C. Mixing with a solvent or the like is preferably performed for about 0.5 to 5 hours. Surfactant, solubilizer or solid carrier is blended in an amount of about 0.1 wt% to 10 wt%, 0.1 wt% to 10 wt%, and 30 wt% to 95 wt%, respectively, with respect to the total amount of the composition. can do.

  The antibacterial agent for industrial use according to the present invention is not limited to the antibacterial activity and stability of the composition, and other antibacterial and antifungal agents, as well as pH adjusters, antioxidants, Additives generally used in the formulation, such as a light stabilizer and an antifoaming agent, can be added.

  The industrial antibacterial agent of the present invention has good antibacterial activity against molds. Specific examples of molds for which the industrial antibacterial agent of the present invention is effective include Aspergillus genus (Aspergillus), Penicillium genus (Aokabi), Cladosporium genus (Black mold), Aureobasidium (Aureobasidium) genus, Alternaria genus (Suscabi), Mucor genus, Gliocladium genus etc. are mentioned.

  In the industrial antibacterial agent of the present invention, when the above antibacterial compound is used in combination, the antibacterial spectrum is wider than when flusilazole or a salt thereof is used alone, not only against molds, but also against bacteria and yeasts. Also has a wide and good antibacterial activity. Examples of the bacteria include Gram-negative bacilli such as Escherichia coli, Pseudomonas aeruginosa, and Serratia; Gram-positive bacilli such as Clostridium; Gram-negative cocci such as planhamella; Gram-positive cocci such as Staphylococcus aureus Are protozoan fungi such as Schizosaccharomyces genus, Protomyces genus, Taphrina genus; elastocyst fungi such as Endomyces genus; semi-genus such as Saccharomyces genus Ascomycetes; Incomplete form of Ascomycetes yeast such as Candida genus; Atypical basidiomycetes such as Filobasidiella; Rhodotorula genus, Trichosporon genus, Sporobolomyces ) Incomplete type of basidiomycetous yeast such as genus; Rhodosporidium genus, Sporidiobolus genus, Xanthone Firomisesu (Xanthophyllomyces) genus Basidiomycetes yeast, etc., and the like.

  Therefore, the industrial antibacterial agent of the present invention can be used for various industrial waters such as paper pulp mills, cooling water circulation processes, coated papers, paper coating liquids, paints, adhesives, synthetic rubber latex, printing inks, plastic products. It can be effectively used for controlling harmful microorganisms in various industrial products such as cement admixtures and sealing agents. More specifically, antibacterial and antifungal agents such as slime control agents for paper pulp mills and cooling water circulation processes, antibacterial and antifungal agents for paper products and resin products, paints, synthetic rubber latex, resins, inks, silicone sealants, etc. Useful as such.

  The industrial antibacterial agent of the present invention may be selected as appropriate depending on the target of application, the type of microorganism (bacteria, mold, yeast, algae, etc.) and the control period. For example, as a slime control agent When used as an antibacterial component amount per kg of product, 0.1 to 500 mg, preferably 0.5 to 100 mg. When used as a preservative, as an antibacterial component amount per kg of product. 1 to 5,000 mg, preferably 10 to 1,000 mg, when used as an antifungal or algae, 10 to 50,000 mg as an amount of antibacterial component per kg of product, preferably 100 to What is necessary is just to add so that it may become 10,000 mg.

  Hereinafter, the present invention will be described in detail with reference to examples.

[Example 1]
Add flusilazole (methylbis (4-fluorophenyl) (1H-1,2,4-triazol-1-ylmethyl) silane; manufactured by Wako Pure Chemical Industries, Ltd.) to methyl carbitol so as to be 10% by weight. (Table 2 described later) was prepared by stirring and mixing at room temperature for 30 minutes to obtain an industrial antibacterial agent which is a white suspension.

  About Example 1, Example 2-28 mentioned later, and Comparative Examples 1-9, antibacterial activity was evaluated by the method shown below. That is, as the test bacteria, Bacillus subtilis IFO3513, Staphylococcus aureus IFO12732, Escherichia coli IFO3972, Pseudomonas aeruginosa IFO3080, Serratia marcescens IFO3735 As for fungi, black mold (Aspergillus niger IFO6341), blue mold (Penicillium citrinum IFO6352), cladosporium cladosporioides (Cladosporium cladosporioides IFO6348), Aureobasidium pullulans IFO6353, Alternaria sp. , Mucor spinescens (Mucor spinescens IFO6071), Gliocladium virens IFO6355, yeasts using Rhodotorula rubra IFO0907, Saccharomyces cerevisiae IFO0209 And comparison In addition suspensions each glucose broth agar medium (pH 6.0) according to, using a micro planter (Sakuma Seisakusho) was inoculated with inoculum for the bacterial suspensions were incubated for 18 hours at 33 ° C.. In the case of molds and yeasts, in the same manner as described above, inoculate the fungal spore suspension or the yeast suspension for inoculation on the glucose broth agar medium (pH 6.0) to which Examples and Comparative Examples were respectively added. The cells were cultured at 33 ° C. for 18 hours, and further cultured at 28 ° C. for 2 days. After the cultivation, the growth of each bacterium was observed to determine the minimum inhibitory concentration (MIC) (μg / mL). The results of Example 1 are shown in Table 1.

  As is clear from Table 1, the industrial antibacterial agent of Example 1 exhibited a MIC of 50 μg / mL or less against molds, indicating that it had good antibacterial activity.

[Examples 2 to 28]
The compositions of Examples 2 to 28 of the industrial antibacterial agent according to the present invention are shown in Table 2, and the compositions of Comparative Examples 1 to 9 are shown in Table 3. In the following Examples and Comparative Examples, the same flusilazole manufactured by Wako Pure Chemical Industries, Ltd. was used.

  Examples of the isothiazoline-based compound include “ZONEN-MT” (containing 50% by weight of 2-methyl-4-isothiazolin-3-one, manufactured by Chemicrea Co., Ltd.), “Caisson WT” (2-methyl-4-isothiazoline-3-one). And 14% by weight of a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one, manufactured by Rohm and Haas), “Caisson 893T” (2-n-octyl-4-isothiazolin-3-one 99. 5% by weight, manufactured by Rohm and Hers) was used.

  As the benzisothiazoline compound, “BIT” (containing 80% by weight of 1,2-benzisothiazolin-3-one, manufactured by Dow Chemical Company) was used.

  As the haloacetylene compound, “Troysan polyphase P-100” (containing 99.4% by weight of 3-iodo-2-propynyl N-butyl carbamate, manufactured by Troy Chemical Co., Ltd.) was used.

  As the carbamoylimidazole compound, “prochloraz” (N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] -1H-imidazole-1-carboxamide) (manufactured by Wako Pure Chemical Industries, Ltd.) Was used.

  As the alkoxyalkylamine compound, 3-dodecyloxypropylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was used.

  As the tetrahydrothiophene dioxide compound, a 20% by weight diethylene glycol monomethyl ether solution (manufactured by Nippon Enviro Chemicals Co., Ltd.) of slab curve (3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide) was used.

  As quinolone compounds, oxolinic acid (5-ethyl-5,8-dihydro-8-oxo-1,3-dioxolo [4,5-g] quinoline-7-carboxylic acid, manufactured by Wako Pure Chemical Industries, Ltd.) Was used.

  Examples and Comparative Examples were prepared according to the compositions shown in Tables 2 and 3 by adding each antibacterial agent component to methyl carbitol and stirring and mixing at room temperature for 30 minutes to obtain a white suspension. .

  Evaluation of antibacterial activity when flusilazole and a predetermined antibacterial compound are used in combination is flusilazole, isothiazoline compound, benzisothiazoline compound, haloacetylene compound, carbamoylimidazole compound, alkoxyalkylamine compound, tetrahydrothiophene dioxide compound And quinolone compounds were used alone (Example 1 and Comparative Examples 1 to 9) from the MIC values, the theoretical values of MIC were calculated by the following formula for each example, and the actually measured MIC values were It was done by comparing with. When the measured value of MIC is smaller than the theoretical value, that is, when “measured value / theoretical value” is smaller than 1, the antibacterial activity is enhanced from the algebraic sum when each of the above components is used alone. Therefore, it was evaluated that a synergistic effect was observed.

Theoretical value of MIC = C _A × x / 100 + C _B × y / 100
C _A ; MIC value when flusilazole is used alone (Example 1) C _B ; isothiazoline compound, benzisothiazoline compound, haloacetylene compound, carbamoylimidazole compound, alkoxyalkylamine compound, tetrahydrothiophene dioxide MIC value when each of the quinolone compound and the quinolone compound is used alone (Comparative Examples 1 to 9) x: the proportion of flusilazole in the antibacterial agent component (%)
y: Ratio of the isothiazoline compound, benzisothiazoline compound, haloacetylene compound, carbamoylimidazole compound, alkoxyalkylamine compound, tetrahydrothiophene dioxide compound or quinolone compound in the antibacterial agent component (%)

  The evaluation results of the antibacterial activity are shown in Tables 4 to 12. "100/0", "75/25", "50/50", "25/75" and "0/100" in each table are flusilazole, an isothiazoline compound, a benzisothiazoline compound, a haloacetylene compound The compounding weight ratio with a compound, a carbamoylimidazole compound, an alkoxyalkylamine compound, a tetrahydrothiophene dioxide compound or a quinolone compound is shown.

  The above Table 4 shows industrial antibacterial agents containing flusilazole and isothiazoline-based compounds in a weight ratio of 100: 0, 75:25, 50:50, 25:75 as 2-methyl-4-isothiazolin-3-one. The evaluation result about (Examples 1-4) is shown. Measured / theoretical value of MIC for Bacillus subtilis, Escherichia coli, Serratia and Cladosporium for Example 2 and Bacillus subtilis for Example 3, Escherichia coli and Mucor spines for Example 4 , And others, synergistic antibacterial activity for each bacterium and mold tested compared to when flusilazole and 2-methyl-4-isothiazolin-3-one were used alone (Example 1 and Comparative Example 1), respectively. The effect was recognized.

  Table 5 above shows that flusilazole and a mixture of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one as isothiazoline-based compounds are 100: 0, 75: The evaluation result about the industrial antibacterial agent (Example 1, 5-7) contained by the weight ratio of 25, 50:50, 25:75 is shown. The measured / theoretical value of MIC for Alternaria for Example 5 and blue mold for Examples 6 and 7 is greater than 1, but the others are flusilazole and 2-methyl-4-isothiazolin-3-one and 5- Synergistic antibacterial activity for each bacterium, mold and yeast tested compared to when each chloro-2-methyl-4-isothiazolin-3-one mixture was used alone (Example 1 and Comparative Example 2). The effect was recognized.

  Table 6 above shows industrial use containing flusilazole and isothiazoline-based compounds in a weight ratio of 100: 0, 75:25, 50:50, 25:75 as 2-n-octyl-4-isothiazolin-3-one. The evaluation result about an antibacterial agent (Example 1, 8-10) is shown. Compared to when flusilazole and 2-n-octyl-4-isothiazolin-3-one were used alone (Example 1 and Comparative Example 3), each composition was tested for each bacterium, mold and yeast tested. On the other hand, a synergistic effect of antibacterial activity was observed.

  Table 7 shows an industrial antibacterial composition containing flusilazole and 3-iodo-2-propynyl N-butyl carbamate as a haloacetylene compound in a weight ratio of 100: 0, 75:25, 50:50, 25:75. The evaluation result about an agent (Example 1, 11-13) is shown. In Example 11, when flusilazole and 3-iodo-2-propynyl N-butylcarbamate were used alone, except that the actual measurement / theoretical value of MIC for Bacillus subtilis was 1, (Example 1 and Comparative Example 4) Compared with, a synergistic effect of antibacterial activity was observed against the tested bacteria, mold and yeast.

  Table 8 shows an industrial antibacterial agent containing flusilazole and 1,2-benzisothiazolin-3-one as a benzisothiazoline compound in a weight ratio of 100: 0, 75:25, 50:50, 25:75. The evaluation result about (Example 1, 14-16) is shown. The measured / theoretical value of the MIC for Pseudomonas aeruginosa, blue mold and glyocladium vilens for Example 14 and blue mold, Rhodotorula rubras and Saccharomyces cerevisiae for Example 16 is greater than 1, but the others are flusilazole and 1, Compared to the case where 2-benzisothiazolin-3-one was used alone (Example 1 and Comparative Example 5), a synergistic effect of antibacterial activity was observed for each bacterium, mold and yeast tested.

  Table 9 shows industrial antibacterial agents containing flusilazole and 3-dodecyloxypropylamine as alkoxyalkylamine compounds in weight ratios of 100: 0, 75:25, 50:50, and 25:75 (Examples). The evaluation result about 1, 17-19) is shown. Example 17 Cladosporium Cladosporioids, Aureobasidium pullulans and Alternaria spp., Example 18 Cladosporium cladosporioids and Alternaria spp., Example 19 Aureobasidium pullulans Except for the actual measurement / theoretical value being 1 or more, each of the tested bacteria, molds and yeasts was compared with the case where flusilazole and 3-dodecyloxypropylamine were each used alone (Example 1 and Comparative Example 6). Thus, a synergistic effect of antibacterial activity was observed.

  Table 10 shows that flusilazole and tetrahydrothiophene dioxide-based compound are slab curve (3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide) at 100: 0, 75:25, 50:50, The evaluation result about the industrial antibacterial agent (Examples 20, 20-22) contained by the weight ratio of 25:75 is shown. In Examples 20 and 21, the measured / theoretical value of MIC for black mold for Example 20 and Aureobasidium pullulans for Example 22 exceeded 1, but in the other cases, flusilazole and slab curve were each used alone (Example 1). Compared with Comparative Example 7), a synergistic effect of antibacterial activity was observed for each bacterium, mold and yeast tested.

  Table 11 shows that 100: 1 of flusilazole and prochloraz (N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] -1H-imidazole-1-carboxamide) as a carbamoylimidazole compound. 75:25, 50:50, Evaluation results for industrial antibacterial agents (Examples 23 to 25) contained at a weight ratio of 25:75 are shown. Regarding Example 25, the measured / theoretical value of MIC for Cladosporium, Cladosporieudes and Mucor spinesens exceeded 1, but in the other cases, when flusilazole and prochloraz were used alone (Example 1 and Comparative Example) Compared to 8), a synergistic effect of antibacterial activity was observed for each bacterium and mold tested.

  Table 12 shows the evaluation results for industrial antibacterial agents (Examples 1, 26 to 28) containing flusilazole and oxolinic acid in a weight ratio of 100: 0, 75:25, 50:50, 25:75. Show. MIC measurements / theory for Staphylococcus aureus, E. coli and Aureobasidium pullulans for Example 26, for Staphylococcus aureus, Escherichia coli, Cladosporium cladosporieudes, Aureobasidium pullulans and Alternaria for Example 28 Although the value exceeds 1, the synergistic effect of the antibacterial activity on each of the tested bacteria and fungi compared to when flusilazole and oxolinic acid were used alone (Example 1 and Comparative Example 9), respectively. Was recognized.

  As described above, in the examples of the present invention, it is recognized that flusilazole has antibacterial activity against various molds, and the antibacterial activity is synergistically increased by using a predetermined antibacterial compound together. A broad synergistic effect of antibacterial activity was observed against bacteria and mold and yeast fungi.

  According to the present invention, it is possible to provide an industrial antibacterial agent that can be used in a wide range of industrial applications such as industrial water and control of harmful microorganisms in various industrial products, and whose antibacterial activity is synergistically improved in each of these applications. it can.

Claims (8)

Flucilazole or a salt thereof , an isothiazoline compound represented by formula (1), 1,2- benzisothiazolin -3-one represented by formula (2), a haloacetylene compound represented by formula (3), formula (4) ), A carbamoylimidazole compound represented by formula (5), a tetrahydrothiophene dioxide compound represented by formula (6), a quinolone compound represented by formula (7), and these one or containing two or more, industrial antibacterial agent selected from the group consisting of salts.

[In the formula, _{R 1} represents a linear alkyl group having 1 to 8 carbon atoms, _{R 2} and _{R 3} are the same or different, each represent a hydrogen atom or a halogen atom. ]


[Wherein, X represents a halogen atom, _{R 5} represents an alkyl group having 1 to 4 carbon atoms. ]

[Wherein, R ₇ represents an alkyl group having 1 to 4 carbon atoms, R ₈ represents phenyl substituted with 1 to 3 chlorine atoms, and n represents 2 . ]

Wherein, _{R 9} is shows the one alkyl group having 2 to 4 carbon atoms which is substituted by an alkoxy group 12 to 16 carbon atoms. ]

_Wherein, Y _1, Y 2, _{Y 3} and _{Y 4} are the same or different and each indicates a hydrogen atom or a halogen _atom, all of Y _1, Y 2, _{Y 3} and _{Y 4} is a halogen atom Or Y ₁ , Y ₂ and Y ₃ are halogen atoms and Y ₄ is a hydrogen atom, or Y ₁ and Y ₄ are halogen atoms and Y ₂ and Y ₃ are hydrogen atoms . ]

[ Wherein, R ₁₂ represents an alkyl group having 1 to 4 carbon atoms . ] Isothiazoline-based compounds are 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 5 -Chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one and 4,5-dichloro-2-n-octyl-4-isothiazoline-3 The industrial antibacterial agent according to claim 1 , which is one or more selected from the group consisting of -one. The isothiazoline-based compound is selected from the group consisting of 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-n-octyl-4-isothiazolin-3-one The industrial antibacterial agent according to claim 1 , which is one or more selected. The industrial antibacterial agent according to claim 1 , wherein the haloacetylene compound is 3-iodo-2-propynyl N-butyl carbamate. The industrial antibacterial agent according to claim 1 , wherein the carbamoylimidazole compound is N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] -1H-imidazole-1-carboxamide. The industrial antibacterial agent according to claim 1 , wherein the alkoxyalkylamine compound is 3-dodecyloxypropylamine or a salt thereof. The industrial antibacterial agent according to claim 1 , wherein the tetrahydrothiophene dioxide-based compound is 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. The industry according to claim 1 , wherein the quinolone compound is 5-ethyl-5,8-dihydro-8-oxo-1,3-dioxolo [4,5-g] quinoline-7-carboxylic acid or a salt thereof. Antibacterial agent.