JP2010173972A - Antimicrobial composition for industrial use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antimicrobial composition for industrial use applicable to a wide range of industrial applications, and having high antimicrobial activity in their applications. <P>SOLUTION: The antimicrobial composition for industrial use applicable to a wide range of industrial applications is such as to be obtained by using, in combination, oxolinic acid or a salt thereof with one compound or two or more compounds in combination selected from the group consisting of an isothiazoline-based compound, benzisothiazoline-based compound, benzimidazole-based compound, haloacetylene-based compound, carbamoylimidazole-based compound, alkyloxyalkylamine-based compound, and tetrahydrothiophene dioxide-based compound, effecting synergistically improving its antimicrobial activity. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an industrial antibacterial composition having a synergistically enhanced antibacterial effect, and more particularly to an industrial antibacterial composition comprising an oxolinic acid or a salt thereof and a predetermined antibacterial compound in combination.

  Oxolinic acid is 5-ethyl-5,8-dihydro-8-oxo [1,3] dioxolo [4,5-g] quinoline-7-carboxylic acid, its antibacterial properties, production method, physical properties, formulation There are reports on metabolism and toxicity (Non-patent Document 1). In addition to controlling bacterial plant diseases, oxolinic acid is widely used for antibacterial and antifungal activities in industrial fields such as processing of resin, fiber, paper, and paints. However, sufficient antibacterial activity may not be obtained depending on the object or mode of use.

  In order to enhance the antibacterial activity of oxolinic acid, a combination with other antibacterial agents has been proposed, and a synergistic effect by the combination with zinc oxide has been shown (Patent Document 1). However, since the technique described in the above-mentioned patent document contains zinc oxide which is a powder, it is provided in the form of a wettable powder, a flowable agent or a powder, or a dilute solution thereof with water. There are cases where it is difficult to use depending on the object and the mode of use of the antibacterial agent, and there are cases where a sufficient antibacterial effect cannot be obtained. Therefore, an industrial antibacterial composition that can be widely used for industrial applications and has more effective antibacterial activity has been desired.

JP 2002-284601 A

Sumitomo Chemical 1993-II pp.4-21

  Therefore, an object of the present invention is to obtain an industrial antibacterial composition that can be used in a wide range of industrial applications and has good antibacterial activity in each of those applications.

  As a result of intensive studies to solve the above problems, the present inventor has found that oxolinic acid or a salt thereof, an isothiazoline compound, a benzisothiazoline compound, a benzimidazole compound, a haloacetylene compound, a carbamoylimidazole compound, an alkyloxy When used in combination with one or more selected from the group consisting of alkylamine compounds and tetrahydrothiophene dioxide compounds, a synergistic increase in antibacterial activity can be seen, and it can be used in various modes. Thus, the inventors have found that an industrial antibacterial composition that can be used for a wide range of industrial applications can be obtained, and have completed the present invention.

That is, the present invention relates to the following [1] to [16].
[1] A group consisting of oxolinic acid or a salt thereof, an isothiazoline compound, a benzisothiazoline compound, a benzimidazole compound, a haloacetylene compound, a carbamoylimidazole compound, an alkyloxyalkylamine compound, and a tetrahydrothiophene dioxide compound An antibacterial composition for industrial use, comprising one or more selected from the group consisting of:
[2] The industrial antibacterial composition according to [1], wherein the isothiazoline-based compound is a compound represented by the following formula (1).

[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. ]

[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 composition according to the above [1] or [2], 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 composition according to the above [1] or [2], which is one or two selected.
[5] The industrial antibacterial composition according to any one of [1] to [4], wherein the benzisothiazoline-based compound is a compound represented by the following formula (2).

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

[6] The above [1] to [5], wherein the benzisothiazoline-based compound is one or two selected from 1,2-benzisothiazolin-3-one and Nn-butyl-benzisothiazolin-3-one. ] The industrial antibacterial composition in any one of.

[7] The industrial antibacterial composition according to any one of [1] to [6], wherein the benzimidazole compound is a compound represented by the following formula (3).

[Wherein, ring A ₂ represents an optionally substituted benzene ring, and Z represents —NHCOOR ₄ (wherein R ₄ represents a hydrogen atom or an alkyl group) or a substituted group. A good 5- or 6-membered nitrogen-containing heterocyclic group is shown. ]

[8] The above [1], wherein the benzimidazole compound is one or more selected from the group consisting of methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate, and 2- (4-thiazolyl) benzimidazole. ] The industrial antibacterial composition according to any one of [7] to [7].
[9] The industrial antibacterial composition according to any one of the above [1] to [8], wherein the haloacetylene compound is a compound 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. ]

[10] The industrial antibacterial composition according to any one of [1] to [9], wherein the haloacetylene-based compound is 3-iodo-2-propylbutylcarbamate.
[11] The industrial antibacterial composition according to any one of the above [1] to [10], wherein the carbamoylimidazole compound is a compound 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. ]

[12] The above [1] to [11], wherein the carbamoylimidazole compound is 1-N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] carbamoylimidazole. Industrial antibacterial composition.
[13] The industrial antibacterial composition according to any one of [1] to [12], wherein the alkyloxyalkylamine compound is a compound represented by the following formula (6).

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

[14] The industrial antibacterial composition according to any one of [1] to [13], wherein the alkyloxyalkylamine-based compound is 3-dodecyloxypropylamine.
[15] The industrial antibacterial composition according to any one of [1] to [14], wherein the tetrahydrothiophene dioxide compound is a compound 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. ]

[16] The industrial antibacterial composition according to any one of [1] to [15], wherein the tetrahydrothiophene dioxide compound is 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. object.

  According to the present invention, an antibacterial activity increases synergistically, and an excellent industrial antibacterial composition that can be used for a wide range of industrial applications can be obtained.

  The oxolinic acid used in the industrial antimicrobial composition according to the present invention has the chemical name 5-ethyl-5,8-dihydro-8-oxo [1,3] dioxolo [4,5-g] quinoline-7-carboxylic acid. For example, the antibacterial compound described in The Pesticide Manual 10th edition (British Crop Protection Council), page 760. Oxolinic acid may be used in the form of an alkali metal salt such as sodium salt or potassium salt, an alkaline earth metal salt such as magnesium salt or calcium salt, or an alkylamine salt such as ammonium salt or trimethylamine salt.

  The industrial antibacterial composition according to the present invention comprises the above oxolinic acid or a salt thereof, an isothiazoline compound, a benzisothiazoline compound, a benzimidazole compound, a haloacetylene compound, a carbamoylimidazole compound, an alkyloxyalkylamine compound. And one or more selected from the group consisting of tetrahydrothiophene dioxide compounds.

  Examples of the isothiazoline-based compound used in the industrial antibacterial composition according to the present invention include a compound represented by the formula (1).

[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 (1), the hydrocarbon group of the optionally substituted hydrocarbon group represented by R ₁ is preferably a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms. 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, sec-pentyl, tert-pentyl (neopentyl), n-hexyl, C1-C10 alkyl groups such as isohexyl, 2-ethylbutyl, n-heptyl, isoheptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, 2-ethylhexyl, nonyl, decyl, preferably 1 to 1 carbon 8 alkyl groups.

  Examples of the alkenyl group include 2 carbon atoms such as ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl and the like. -4 alkenyl groups.

  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 and the like. 5 alkynyl groups.

  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 which may be contained in the optionally substituted hydrocarbon group represented by R ₁ include a halogen atom such as a hydroxyl group, chlorine, fluorine, bromine and iodine, a cyano group, an amino group, a carboxyl group, methoxy, ethoxy, C1-C4 alkoxy group such as propoxy and butoxy, C6-C20 such as phenoxy group, preferably C6-C10 aryloxy group, C1-C4 such as methylthio, ethylthio, propylthio, butylthio And an alkylthio group having 6 to 20 carbon atoms such as a phenylthio group. In the hydrocarbon group represented by R ₁ , these substituents may be the same or different and may contain 1 to 5, preferably 1 to 3.

The optionally substituted hydrocarbon group represented by R ₁ is preferably an unsubstituted hydrocarbon group, and among them, an alkyl group is preferred. 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, and tert-butyl, and An alkyl group having 8 carbon atoms such as n-octyl, isooctyl, sec-octyl, tert-octyl, 2-ethylhexyl is more preferable, and methyl, n-butyl, and n-octyl are more preferable.

In formula (1), examples of the halogen atom represented by R ₂ or R ₃ include fluorine, chlorine, bromine and iodine. Among these, chlorine is preferred.

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. Non-hydrocarbon groups are preferred, and alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl are particularly preferred.

  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, 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-one 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, 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. These isothiazoline compounds may be used alone or in combination of two or more.

  Examples of the benzisothiazoline compound used in the industrial antibacterial composition according to the present invention include a compound represented by the following formula (2).

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

In the above formula (2), the substituent that may be contained in the optionally substituted benzene ring represented by A ₁ ring may be contained in the above-described optionally substituted hydrocarbon group represented by R _1. The thing similar to a substituent can be mentioned, A C1-C4 alkyl group, such as a halogen atom and methyl, ethyl, propyl, and butyl, is mentioned as a preferable thing. These substituents may be the same or different and may be contained in 1 to 4, preferably 1 or 2 in the benzene ring represented by A ₁ ring. As the benzene ring which may be substituted represented by A ₁ ring, a benzene ring is preferably unsubstituted.

In the above formula (2), 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. Hydrocarbon groups that are not formed are preferred, and alkyl groups having 1 to 8 carbon atoms are particularly preferred.

  Specific examples of the benzisothiazoline-based compound include 1,2-benzisothiazoline-3-one and Nn-butyl-1,2-benzisothiazoline-3-one.

  Examples of the benzimidazole compound used in the industrial antibacterial composition according to the present invention include compounds represented by the following formula (3).

[Wherein, ring A ₂ represents an optionally substituted benzene ring, and Z represents —NHCOOR ₄ (wherein R ₄ represents a hydrogen atom or an alkyl group) or a substituted group. A good 5- or 6-membered nitrogen-containing heterocyclic group is shown. ]

In the above formula (3), the substituent that may be contained in the optionally substituted benzene ring represented by the A ₂ ring is the hydrocarbon group optionally having the substituent represented by R ₁ described above. The thing similar to the substituent which may be included can be mentioned, A C1-C4 alkyl group, such as a halogen atom and methyl, ethyl, propyl, butyl, is mentioned as a preferable thing. These substituents may be the same or different, 1 to 4 to the benzene ring represented by A ₂ ring, preferably may include one or two. As the benzene ring which may be substituted represented by A ₂ ring, a benzene ring is preferably unsubstituted.

In the group represented by —NHCOOR ₄ represented by Z in the above formula (3), examples of the alkyl group represented by R ₄ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert -Alkyl groups having 1 to 8 carbon atoms such as butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl are mentioned. Among them, 1 to C carbon atoms such as methyl, ethyl, n-propyl and the like. The alkyl group of 3 is particularly preferred.

  In the above formula (3), the optionally substituted 5- or 6-membered nitrogen-containing heterocyclic group represented by Z contains 1 to 4 nitrogen atoms as ring constituent atoms, or 1 to 2 A 5- or 6-membered monocyclic heterocyclic group containing one nitrogen atom in addition to oxygen and sulfur as a ring-constituting atom, or the 5- or 6-membered nitrogen-containing heterocyclic ring And a condensed heterocyclic group in which a benzene ring or a 5-membered ring is condensed. Examples of the 5- or 6-membered nitrogen-containing monocyclic heterocyclic group include pyridyl groups such as 2-pyridyl, 3-pyridyl and 4-pyridyl, thiazolyl groups such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, 3- Isothiazolyl groups such as isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, imidazolyl groups such as 5-imidazolyl, pyrrolyl groups such as 2-pyrrolyl, 3-pyrrolyl, 2-pyrrolinyl, Pyrrolidinyl groups such as 3-pyrrolinyl, pyrrolinyl groups such as 1-pyrrolidinyl, 2-pyrrolidinyl, pyrrolidinyl groups such as 3-pyrrolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 5-imidazolidinyl And pyrazolyl such as 5-pyrazolyl Oxazolyl groups such as 2-oxazolyl, 4-oxazolyl and 5-oxazolyl, isoxazolyl groups such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, tetrazolyl groups such as 1H-tetrazolyl and 2H-tetrazolyl, 2-pyrimidyl, 4 -Pyrimidyl groups such as pyrimidyl and 5-pyrimidyl, pyridazinyl groups such as 3-pyridazinyl and 4-pyridazinyl, pyrazinyl groups such as 2-pyrazinyl, 3-pyrazinyl, 5-pyrazinyl and 6-pyrazinyl, 2-thiazinyl and 3-thiazinyl A thiazinyl group such as 5-thiazinyl and 6-thiazinyl; a piperazinyl group such as 2-piperazinyl, 3-piperazinyl, 5-piperazinyl and 6-piperazinyl; 2-thiadiazinyl; 3-thiadiazinyl; Thiadiazyl groups such as 1,3,4-oxadiazolyl, oxadiazolyl groups such as 3- or 5- (1,2,4-oxadiazolyl), and thiadiazolyl groups such as 4- or 5- (1,2,3-thiadiazolyl) 1,2,3-triazolyl, 1,2,4-triazolyl and the like triazolyl groups, 2-thiomorpholinyl, 3-thiomorpholinyl, 5-thiomorpholinyl, 6-thiomorpholinyl and the like thiomorpholinyl groups, 2-morpholinyl, 3-morpholinyl, 5 -Morpholinyl group such as morpholinyl, 6-morpholinyl, oxoimidazolinyl group such as 2-oxoimidazolinyl, 1,2,4-triazin-3,5-dione-1-yl, 1,2,4 -Dioxotri, such as triazine-3,5-dione-2-yl, 1,2,4-triazin-3,5-dione-4-yl Examples include azinyl group, piperidinyl group such as 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 5-piperidinyl, and 6-piperidinyl, and piperazinyl groups such as 2-piperazinyl, 3-piperazinyl, 4-piperazinyl, and 5-piperazinyl. . Examples of the condensed heterocyclic group include quinolyl groups such as 2-quinolyl, 3-quinolyl and 4-quinolyl, isoquinolyl groups such as 3-isoquinolyl and 4-isoquinolyl, indolyl groups such as 2-indolyl and 3-indolyl, and 1H- Isoindolyl groups such as isoindol-3-yl, quinolidinyl groups such as 8-quinolidinyl, purinyl groups such as 1H-purin-6-yl, 3H-purin-6-yl, and cinnolinyl groups such as 3-cinnolinyl and 5-cinnolinyl Indazolyl groups such as 3-indazolyl, pteridinyl groups such as 2-pteridinyl, phthalazinyl groups such as 4-phthalazinyl, quinazolinyl groups such as 2-quinazolinyl and 4-quinazolinyl, quinoxalinyl groups such as 2-quinoxalinyl and 3-quinoxalinyl, 2 An indolizinyl group such as indolizinyl, 2H-1,3-benzene Benzooxazinyl group such as zooxazin-2-yl, phenothiazinyl group such as 2-phenothiazinyl, 3-phenothiazinyl, phenazinyl group such as 2-phenazinyl, 3-phenazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4- Examples include phenoxazinyl groups such as phenoxazinyl. Of the above heterocyclic groups, preferred are 5-membered nitrogen-containing heterocyclic groups, with thiazolyl groups being particularly preferred.

  Examples of the substituent that may be contained in the heterocyclic ring include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, Alkoxy groups having 1 to 4 carbon atoms such as ethoxy, n-propoxy, isopropoxy, butoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, halogen atoms such as fluorine, chlorine and bromine, hydroxyl groups, amino groups, A nitro group, a mercapto group, etc. are mentioned.

  Specific examples of the benzimidazole compound include methyl 2-imidazole carbamate, ethyl 2-imidazole carbamate, and 2- (4-thiazolyl) benzimidazole. In the present invention, salts of these compounds can also be used. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, inorganic acid salts such as hydrochloride, nitrate and phosphate, organic acid salts such as paratoluene sulfonate and methyl sulfonate, ammonium salt, Examples thereof include salts with organic amines such as ethylenediamine and 1,6-hexamethylenediamine.

  Examples of the haloacetylene compound used in the industrial antibacterial composition according to the present invention include compounds 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, and iodine is particularly preferable.

In the formula (4), examples of the optionally substituted hydrocarbon group represented by R ₅ or R ₆ include the same as the optionally substituted hydrocarbon group represented by R ₁ described above. As such a group, an unsubstituted hydrocarbon group is preferable, and among them, an alkyl group having 1 to 10 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is further preferable, and an n-butyl group is particularly preferable. . Moreover, it is preferable that either of the groups represented by R ₅ or R ₆ is the above-described optionally substituted hydrocarbon group, and the other is a hydrogen atom, and any of the groups represented by R ₅ or R ₆ Is more preferably the alkyl group and the other is a hydrogen atom.

  In 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 and N-methyl-3-chloropropiool as acid amide derivatives of haloacetylene compounds in the case where m is 0 in formula (4). Acid amide, N-ethyl-3-chloropropiolic acid amide, N-propyl-3-chloropropiolic acid amide, N-butyl-3-chloropropiolic acid amide, N-hexyl-3-chloropropiolic acid amide N-octyl-3-chloropropiolic acid amide, N-cyclohexyl-3-chloropropiolic acid amide and the like (N-substituted-) 3-chloropropiolic acid amide, 3-bromopropiolic acid amide, N- Methyl-3-bromopropiolic amide, N-ethyl-3-bromopropiolic amide, N-propyl-3-bromopro All acid amide, N-butyl-3-bromopropiolic acid amide, N-hexyl-3-bromopropiolic acid amide, N-octyl-3-bromopropiolic acid amide, N-cyclohexyl-3-bromopropiolic acid (N-substituted-) 3-bromopropiolic acid amide, 3-iodopropiolic acid amide, N-methyl-3-iodopropiolic acid amide, N-ethyl-3-iodopropiolic acid amide, N -Propyl-3-iodopropiolic amide, N-butyl-3-iodopropiolic amide, N-hexyl-3-iodopropiolic amide, N-octyl-3-iodopropiolic amide, N-cyclohexyl (N-substituted-) 3-iodopropiolic amides such as -3-iodopropiolic amide That. Of these, (N-substituted-) 3-iodopropiolic acid amide is preferable, and N-butyl-3-iodopropiolic acid amide is more preferable.

  Moreover, as a carbamate derivative of a haloacetylene compound when m is 1 in formula (4), 3-iodo-2-propynylmethyl carbamate, 3-iodo-2-propynylethyl carbamate, 3-iodo-2 -3-iodo- such as propynylpropyl carbamate, 3-iodo-2-propynylbutyl carbamate, 3-iodo-2-propynyl hexyl carbamate, 3-iodo-2-propynyl octyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate Examples thereof include 2-propynylalkyl carbamate, and 3-iodo-2-propynylbutyl carbamate is preferable. These haloacetylene compounds may be used alone or in combination of two or more.

  Examples of the carbamoylimidazole compound used in the industrial antibacterial composition according to the present invention include compounds 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), examples of the optionally substituted hydrocarbon group represented by R ₇ or R ₈ include the same as the optionally substituted hydrocarbon group represented by R ₁ described above. The group represented by R ₇ is preferably an unsubstituted hydrocarbon group, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and n-propyl. The group is particularly preferred. The group represented by R ₈ is preferably a substituted aryl group, more preferably a phenyl group substituted by 1 to 3 chlorine atoms, and a phenyl group substituted by 3 chlorine atoms. Is more preferable. In said formula (5), n shows the integer of 1-6, Preferably it is 2 or 3.

  Examples of the carbamoylimidazole compound include 1-N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] carbamoylimidazole.

  Examples of the alkyloxyalkylamine compounds used in the industrial antibacterial composition according to the present invention include compounds represented by the following formula (6).

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

In the above formula (6), examples of the alkyl group of the “alkyl group substituted by one or more alkyloxy groups” represented by R ₉ include alkyl groups having 1 to 6 carbon atoms, and among them, An alkyl group having 2 to 4 carbon atoms is preferred. Examples of the alkyloxy group substituted on the alkyl group include an alkyloxy group having 10 to 20 carbon atoms, and among them, an alkyloxy group having 12 to 16 carbon atoms is preferable. Examples of the alkyl group represented by R ₁₀ or R ₁₁ include alkyl groups having 1 to 6 carbon atoms, and these groups are preferably both hydrogen.

  As said alkyloxyalkylamine type compound, 3-dodecyloxypropylamine is mentioned as a preferable thing.

  Examples of the tetrahydrothiophene dioxide compound used in the industrial antibacterial composition according to the present invention include compounds 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 the above formula (7), examples of the halogen atom represented by Y ₁ , Y ₂ , Y ₃ or Y ₄ include fluorine, chlorine, bromine and iodine, with chlorine being particularly preferred. The optionally substituted hydrocarbon group represented by Y ₁ , Y ₂ , Y ₃ or Y ₄ is the same as the optionally substituted hydrocarbon group represented by R ₁ described above. A lower alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like is preferable.

Examples of the compound represented by the above formula (7), _Y 1 in the _formula, Y 2, all _{Y 3} and _{Y 4} is a halogen atom _compound, Y 1, _{Y 2} and _{Y 3} is _{Y 4} with a halogen atom A compound in which is a hydrogen atom, and a compound in which Y ₁ and Y ₄ are halogen atoms and Y ₂ and Y ₃ are hydrogen atoms are preferred. Of these, compounds in which all of Y ₁ , Y ₂ , Y ₃ and Y ₄ are halogen atoms, and particularly compounds in which all of Y ₁ , Y ₂ , Y ₃ and Y ₄ are chlorine atoms are preferred.

  Specifically, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, 3,3,4,4-tetrabromotetrahydrothiophene-1,1-dioxide, 3,4-dichlorotetrahydro Examples include thiophene-1,1-dioxide, 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide, 3,3,4-tribromotetrahydrothiophene-1,1-dioxide, and among these, 3 4,4-tetrachlorotetrahydrothiophene-1,1-dioxide is particularly preferred.

  The above oxolinic acids or salts thereof, isothiazoline compounds, benzisothiazoline compounds, benzimidazole compounds, haloacetylene compounds, carbamoylimidazole compounds, alkyloxyalkylamine compounds and tetrahydrothiophene dioxide compounds are known compounds. Or can be prepared from known compounds according to known techniques, many of which are already commercially available from various companies. In the present invention, it is convenient to use such a commercial product.

  In order to obtain sufficient antibacterial activity in the industrial antibacterial composition according to the present invention, oxolinic acid or a salt thereof, an isothiazoline compound, a benzisothiazoline compound, a benzimidazole compound, a haloacetylene compound, a carbamoylimidazole compound , One or two or more selected from the group consisting of alkyloxyalkylamine compounds and tetrahydrothiophene dioxide compounds are preferably contained in a weight ratio of 9: 1 to 1: 9. Further, it is preferably contained in a weight ratio of 8: 2 to 2: 8. In addition, depending on the dosage form of the composition, the target to which antibacterial activity is imparted, the environment in which it is used, etc., the oxolinic acid or salt thereof is 0.1 wt% to 40 wt%, based on the total weight of the composition, One or more selected from the group consisting of isothiazoline compounds, benzisothiazoline compounds, benzimidazole compounds, haloacetylene compounds, carbamoylimidazole compounds, alkyloxyalkylamine compounds and tetrahydrothiophene dioxide compounds , Preferably 0.1 to 40% by weight. Moreover, it is preferable to contain so that these total amounts may be 0.2 weight%-80 weight%, and it is more preferable to contain so that it may become 0.5 weight%-50 weight%.

  The antibacterial composition for industrial use according to the present invention is dissolved in a solvent or suspended or dispersed using a surfactant or a solubilizing agent, etc., as a liquid agent, a suspending agent or a dispersing agent, or by a surfactant. It can be emulsified and provided as an emulsion. In addition, a surfactant or a solid carrier can be added to provide a wettable powder, flowable powder, powder or 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. Is mentioned. These solvents may be used alone or in combination of two or more. Among 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 alkyl ester, polyoxyethienonyl phenyl ether, polyoxyethylene polyoxypropylene glycol, and alkyl sulfate. 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 solubilizing agents 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, octyldodecanol, oleyl alcohol, and the like. Examples include alcohols, 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 kaolin clay, attapulgite clay, bentonite, montmorillonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, and other natural substances, corn cob flour, walnut shell flour, and other natural substances. Examples thereof include organic substances, synthetic organic substances such as urea, salts such as calcium carbonate and ammonium sulfate, and fine powders or granules of synthetic inorganic substances such as synthetic hydrous silicon oxide.

  The antibacterial agent composition according to the present invention is preferably prepared at 5 ° C to 40 ° C. Mixing with a solvent or the like is preferably performed for about 0.5 to 5 hours. In the case of using a surfactant, a solubilizer, and a solid carrier, the amount added to the total amount of these compositions is 0.1 wt% to 10 wt%, 0.1 wt% to 10 wt%, and 30 wt% to 30 wt%, respectively. About 95% by weight.

  Furthermore, the industrial antibacterial composition according to the present invention includes other antibacterial and antifungal agents, anti-algae agents, etc., pH adjusters, oxidation agents, and the like within a range that does not affect the antibacterial activity and stability of the composition. Additives generally used for formulation, such as an inhibitor, a light stabilizer, and an antifoaming agent, can be added.

  Industrial antibacterial compositions according to the present invention 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, etc. It exhibits a wide range of antibacterial activity against various fungi such as bacteria, black mold and yeast. Further, in the industrial antibacterial composition according to the present invention, oxolinic acid or a salt thereof, or an isothiazoline compound, a benzisothiazoline compound, a benzimidazole compound, a haloacetylene compound, a carbamoylimidazole compound, an alkyloxyalkylamine compound And a synergistic improvement in antibacterial activity as compared with the case where one or two or more selected from the group consisting of tetrahydrothiophene dioxide compounds are used singly, so that each of the above components is contained at a low concentration. Even when used, sufficient antibacterial activity can be obtained.

  Accordingly, the industrial antibacterial composition according to the present invention includes various industrial waters such as a paper pulp factory and a cooling water circulation process, coated paper, paper coating liquid, paint, adhesive, synthetic rubber latex, printing ink, It can be effectively used for controlling harmful microorganisms in various industrial products such as plastic products, 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, and silicone sealants It is useful as such.

  The industrial antibacterial composition according to the present invention may be appropriately selected depending on the application target, the type of microorganism (bacteria, mold, yeast, algae, etc.) and the control period. For example, slime control When used as an agent, the amount of the antibacterial component per kg of product is 0. 1 to 500 mg, preferably 0.5 to 100 mg, when used as a preservative, 1 to 5000 mg, preferably 10 to 1000 mg, fungicide or algaeproof agent as the amount of antibacterial component per kg of product When used as, the amount of the antibacterial agent component per 1 kg of the product is 10 to 50000 mg, preferably 100 to 10000 mg.

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

  The compositions of Examples 1 to 27 of the industrial antibacterial composition according to the present invention are shown in Table 1, and the compositions of Comparative Examples 1 to 10 are shown in Table 2. In the following examples and comparative examples, Wako Pure Chemical Industries, Ltd. was used as the oxolinic acid. 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. As a benzisothiazoline-based compound, “BIT” (containing 1,2-benzisothiazolin-3-one 80% by weight, manufactured by Dow Chemical Co., Ltd.) was used. As the benzimidazole compound, “Carbendazin-G” (methyl 2-benzimidazole carbamate, manufactured by Yokotsusho Co., Ltd.) is used. As the haloacetylene compound, “Troysan polyphase P-100” (3-iodo- 2-propynylbutylcarbamate 99.4% by weight, manufactured by Troy Chemical Co., Ltd. was used as a carbamoylimidazole compound as “prochloraz” (N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl). ] Imidazole-1-carboxamide) (manufactured by Wako Pure Chemical Industries, Ltd.), 3-dodecyloxypropylamine as the alkyloxyalkylamine compound, and Suracap (3, 3, 4,4-tetrachlorotetrahi Rochiofen-1,1-dioxide) using 20 wt% diethylene glycol monomethyl ether solution (manufactured by Japan EnviroChemicals Chemicals Corporation) of.

  Examples and Comparative Examples were prepared according to the compositions shown in Tables 1 and 2 by adding each antibacterial agent component to methyl carbitol and stirring and mixing at room temperature for 30 minutes to obtain a white suspension. .

About an Example and a comparative example, antibacterial activity was evaluated by the method shown below. Specifically , Bacillus subtilis , Staphylococcus aureus , Escherichia coli , Pseudomonas aeruginosa , and Serratia marcescens are used as fungi, and black mold is used as fungi. (A spergillus niger), blue mold (Penicillium citrinum), Cladosporium class dos polio Lee Death (Cladosporium cladosporioides), Out Leo Basi di Umm pullulans (Aureobasidium pullulans), Alternaria species (Alternaria sp.), Mucor Supinessensu (Mucor s pinescens) the Gliocladium Birensu (Gliocladium virens), using Rhodotorula rubra (Rhodotorula rubra), Saccharomyces cerevisiae (Saccharomyces cerevisiae) in yeasts, in the case of bacteria, adding a suspending agent according to the examples and Comparative examples, respectively Glucose broth agar To pH 6.0), it was inoculated with inoculum for the bacterial suspension using a micro planter (Sakuma Seisakusho), and 18 hours at 33 ° C.. In the case of molds and yeasts, a fungal spore suspension or a yeast suspension for inoculation was inoculated on a glucose broth agar medium (pH 6.0) to which Examples and Comparative Examples were respectively added in the same manner as described above, and 33 ° C. And then 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 antibacterial activity is evaluated by oxolinic acid, isothiazoline compound, benzisothiazoline compound, benzimidazole compound, haloacetylene compound, carbamoylimidazole compound, alkyloxyalkylamine compound or tetrahydrothiophene dioxide compound alone. From the MIC value when used (Comparative Examples 1 to 10), the theoretical value of MIC was calculated by the following formula for each example, and the actually measured MIC value was compared with them. 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 oxolinic acid is used alone (Comparative Example 1) C _B ; isothiazoline compound, benzisothiazoline compound, benzimidazole compound, haloacetylene compound, carbamoylimidazole compound, alkyloxyalkylamine MIC value in the case of using an organic compound or a tetrahydrothiophene dioxide compound alone (Comparative Examples 2 to 10) x: proportion of oxolinic acid in antimicrobial component (%)
y: Ratio of the isothiazoline compound, benzisothiazoline compound, benzimidazole compound, haloacetylene compound, carbamoylimidazole compound, alkyloxyalkylamine compound, or tetrahydrothiophene dioxide compound in the antibacterial agent component (%) )

  The evaluation results of antibacterial activity are shown in Tables 3 to 11. “75/25”, “50/50”, “25/75”, “100/0” and “0/100” in each table are oxolinic acid, isothiazoline compound, benzisothiazoline compound, benzimidazole. The compounding weight ratio with a compound, a haloacetylene compound, a carbamoylimidazole compound, an alkyloxyalkylamine compound or a tetrahydrothiophene dioxide compound is shown.

  Table 3 shows that ZOLIN-MT containing 50% by weight of oxolinic acid and 2-methyl-4-isothiazolin-3-one as an isothiazoline-based compound at a weight ratio of 75:25, 50:50, and 25:75. The evaluation result about the antimicrobial composition (Examples 1-3) to contain is shown. For all the compositions, the measured / theoretical value of MIC was less than 1 against Bacillus subtilis, Staphylococcus aureus, and Escherichia coli, and a synergistic effect of antibacterial activity was observed.

  Table 4 above shows caisson containing 14% by weight of a mixture of oxolinic acid and 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one as isothiazoline-based compounds. The evaluation result about the antimicrobial composition (Examples 4-6) which contains WT by the weight ratio of 75:25, 50:50, 25:75 is shown. Antibacterial activity against each tested bacteria, mold and yeast, except for Example 4 Pseudomonas aeruginosa and Serratia bacteria, Example 6 with respect to Pseudomonas aeruginosa, with a measured / theoretical value of MIC exceeding 1. The synergistic effect was recognized.

  Table 5 above shows that caisson 893T containing 99.5% by weight of oxolinic acid and 2-n-octyl-4-isothiazolin-3-one as an isothiazoline-based compound is 75:25, 50:50, 25:75. The evaluation result about the antimicrobial composition (Examples 7-9) contained by weight ratio is shown. For Example 8, a synergistic effect of antibacterial activity was observed for each bacterium, mold and yeast tested except that the actual / theoretical value of MIC was greater than 1 for S. aureus.

  Table 6 above shows 75:25, 50:50, 25: Troisan polyphase P-100 containing 99.4% by weight of oxolinic acid and haloacetylene-based 3-iodo-2-propynylbutylcarbamate. The evaluation result about the antimicrobial composition (Examples 10-12) contained by the weight ratio of 75 is shown. For Example 12, a synergistic effect of antibacterial activity was observed for each tested bacterium, mold and yeast except that the measured / theoretical value of MIC for Serratia was greater than 1.

  Table 7 shows an antibacterial composition containing oxolinic acid and Carbendazin-G (methyl 2-benzimidazole carbamate) in a weight ratio of 75:25, 50:50, and 25:75 as benzimidazole compounds (Examples). The evaluation result about 13-15) is shown. For Example 15, a synergistic effect of antibacterial activity was observed for each tested bacterium, mold and yeast except that the measured / theoretical value of the MIC was greater than 1 for Rhodotorlabra.

  Table 8 shows an antibacterial composition containing 3-oxodecyloxypropylamine at a weight ratio of 75:25, 50:50, and 25:75 as an oxolinic acid and an alkyloxyalkylamine compound (Examples 16 to 18). ) Shows the evaluation results. Antibacterial against each bacterium, mold and yeast tested except for Example 16 with S. aureus and Pseudomonas aeruginosa and Example 17 with a measured / theoretical value greater than 1 for P. aeruginosa A synergistic effect of activity was observed.

  Table 9 shows that oxalinic acid and a 20% by weight solution of suracap (3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide) as a tetrahydrothiophene dioxide-based compound are 75:25, 50:50. The evaluation result about the antimicrobial composition (Examples 19-21) contained by the weight ratio of 25:75 is shown. For Examples 19 and 20, a synergistic effect of antibacterial activity was observed for each of the bacteria, molds and yeasts tested except that the measured / theoretical value of MIC was greater than 1 for Serratia bacteria.

  Table 10 shows that oxolinic acid and prochloraz (N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] imidazole-1-carboxamide) as a carbamoylimidazole compound are 75:25, 50 : The evaluation result about the antibacterial composition (Examples 22-24) contained by a weight ratio of 50 and 25:75 is shown. Synergistic effect of antibacterial activity against each tested bacterium and mold except that the actual / theoretical value of MIC was greater than 1 for S. aureus and Serratia for Example 22 and Serratia for Example 24 Was recognized.

  Table 11 above contains BIT containing 80% by weight of 1,2-benzisothiazolin-3-one as an oxolinic acid and a benzisothiazoline-based compound in a weight ratio of 75:25, 50:50, 25:75. The evaluation result about an antibacterial composition (Examples 25-27) is shown. A synergistic effect of antibacterial activity was observed for each of the tested bacteria, molds and yeasts except that the measured / theoretical value of MIC was greater than 1 for black mold for Example 25 and Rhodotor labra for Example 27. It was.

  As described above, in the examples of the present invention, a broad synergistic effect of antibacterial activity was recognized against bacteria, fungi and yeast fungi.

  According to the present invention, it is possible to provide an industrial antibacterial composition which can be used for a wide range of industrial applications such as industrial water and control of harmful microorganisms in various industrial products, and in which the antibacterial activity is synergistically improved. Can do.

Claims (16)

  It is selected from the group consisting of oxolinic acid or a salt thereof and isothiazoline compounds, benzisothiazoline compounds, benzimidazole compounds, haloacetylene compounds, carbamoylimidazole compounds, alkyloxyalkylamine compounds, and tetrahydrothiophene dioxide compounds. An antibacterial composition for industrial use, comprising one or more kinds. The industrial antibacterial composition according to claim 1, wherein the isothiazoline-based compound is a compound represented by the following formula (1).

[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. ]   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 composition according to claim 1 or 2, which is one or more selected from the group consisting of -on.   1 wherein 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 composition according to claim 1 or 2, which is a seed or two kinds. The industrial antibacterial composition according to any one of claims 1 to 4, wherein the benzisothiazoline compound is a compound represented by the following formula (2).

[Wherein, ring A ₁ represents an optionally substituted benzene ring, and Y represents a hydrogen atom or an optionally substituted hydrocarbon group. ]   The benzisothiazoline-based compound is one or two selected from 1,2-benzisothiazolin-3-one and Nn-butyl-benzisothiazolin-3-one. 1. The industrial antibacterial composition according to item 1. The industrial antibacterial composition according to any one of claims 1 to 6, wherein the benzimidazole compound is a compound represented by the following formula (3).

[Wherein, ring A ₂ represents an optionally substituted benzene ring, and Z represents —NHCOOR ₄ (wherein R ₄ represents a hydrogen atom or an alkyl group) or a substituted group. A good 5- or 6-membered nitrogen-containing heterocyclic group is shown. ]   The benzimidazole compound is one or more selected from the group consisting of methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate, and 2- (4-thiazolyl) benzimidazole. 8. The industrial antibacterial composition according to any one of 7 above. The industrial antibacterial composition according to any one of claims 1 to 8, wherein the haloacetylene compound is a compound 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. ]   The industrial antibacterial composition according to any one of claims 1 to 9, wherein the haloacetylene compound is 3-iodo-2-propylbutyl carbamate. The industrial antibacterial composition according to any one of claims 1 to 10, wherein the carbamoylimidazole compound is a compound 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. ]   The industry according to any one of claims 1 to 11, wherein the carbamoylimidazole compound is 1-N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] carbamoylimidazole. Antibacterial composition. The industrial antibacterial composition according to any one of claims 1 to 12, wherein the alkyloxyalkylamine-based compound is a compound represented by the following formula (6).

[Wherein, R ₉ is an alkyl group substituted with one or more alkyloxy groups, and R ₁₀ and R ₁₁ are the same or different and each represents hydrogen or an alkyl group. ]   The industrial antibacterial composition according to any one of claims 1 to 13, wherein the alkyloxyalkylamine compound is 3-dodecyloxypropylamine. The industrial antibacterial composition according to any one of claims 1 to 14, wherein the tetrahydrothiophene dioxide-based compound is a compound represented by the following formula (7).

_{Wherein, Y 1, Y 2, Y} 3 and Y ₄ are the same or different and represent a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. ]   The industrial antibacterial composition according to any one of claims 1 to 15, wherein the tetrahydrothiophene dioxide-based compound is 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide.