JP2005298422A - Industrial antimicrobial composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an industrial antimicrobial composition which has sufficient control effects against harmful microorganisms and can reduce the content of an organic solvent to decrease loads on environments. <P>SOLUTION: This industrial antimicrobial composition is characterized by comprising an alkylimidazole-based compound represented by general formula (1) (R<SP>1</SP>is a 1 to 18C hydrocarbon group which may have one or more substituents; R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>are each a 1 to 18C hydrocarbon group which may have one or more substituents or H) and a hydrophobic antibacterial agent and/or a hydrophilic antiseptic, and having a smaller pH value than the pH value of the alkylimidazole-based compound, when diluted with water. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to an industrial sterilizing composition, and more particularly to an industrial sterilizing composition used as a control agent for bacteria, fungi and yeasts.

  Conventionally, for example, various industrial water used in papermaking processes in pulp and paper mills, cooling water circulation processes in various factories, metal processing oils (cutting oil, etc.), casein, starch paste, glue, coated paper, paper coating liquid , Surface sizing agent, paint, adhesive, synthetic rubber latex, ink, polyvinyl alcohol film, vinyl chloride film, resin product, cement admixture, sealing agent, joint agent, etc. for various industrial products such as bacteria, mold, yeast Harmful microorganisms such as these are easy to propagate, causing a decrease in productivity and quality, and the generation of malodors. Therefore, in order to sterilize such harmful microorganisms, industrial sterilizing compositions containing antiseptics and fungicides are widely used.

Further, it is known that alkylimidazole compounds have antibacterial activity (Patent Document 1).
JP-A 51-54925

  However, in recent years, from the viewpoint of environmental load, it is required to use water as a dispersion medium for industrial sterilization compositions to reduce the amount of organic solvents and surfactants used. However, among the known antifungal agents, those having high antifungal performance are often hydrophobic, and therefore it is inevitable to use an organic solvent as a dispersion medium. Moreover, although a hydrophilic thing is known for antiseptic | preservative, when it is going to acquire antifungal performance, it will be necessary to mix | blend the well-known antifungal agent which is hydrophobic.

  The present invention has been made in view of such circumstances, and its purpose is to exhibit a sufficient control effect against harmful microorganisms and reduce the amount of organic solvent used, thereby reducing the burden on the environment. It is to provide an industrial disinfecting composition that can be reduced.

  In order to achieve the above-mentioned object, the present inventors diligently examined the effectiveness of water-solubility that can obtain antiseptic performance and fungicidal performance. As a result of further finding out the findings of solubilization with other active ingredients when the pH value is lower than that of the present invention, the present invention has been completed.

That is, the present invention
(1) including an alkylimidazole compound represented by the following general formula (1), a hydrophobic fungicide and / or a hydrophilic preservative,
The industrial bactericidal composition, wherein the pH value when diluted with water is smaller than the pH value of the alkylimidazole compound,
General formula (1):

(In the formula, R ¹ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. R ² , R ³ and R ⁴ independently have a substituent. A C1-C18 hydrocarbon group or a hydrogen atom may be used.)
(2) The hydrophobic antifungal agent is an isothiazoline compound represented by the following general formulas (2) and (3), a haloacetylene compound represented by the following general formula (4), and the following general formula (5). The industrial sterilizing composition according to (1), characterized in that it is at least one compound selected from the group consisting of benzimidazole compounds shown
General formula (2):

(In the formula, R ⁵ represents an optionally substituted hydrocarbon group having 6 to 12 carbon atoms. R ⁶ and R ⁷ are independently a hydrocarbon group (R ⁶ and R ⁷ are Including a case where a ring is formed by a divalent hydrocarbon group.), A halogen atom or a hydrogen atom.)
General formula (3):

(In the formula, R ⁸ represents a hydrocarbon group or a hydrogen atom which may have a substituent. The A ring represents a benzene ring which may have a substituent.)
General formula (4):

(In the formula, R ⁹ and R ¹⁰ independently represent a hydrocarbon group or a hydrogen atom which may have a substituent. X ¹ represents a halogen atom. M represents an integer of 0 or 1. .)
General formula (5):

(In the formula, R ¹¹ represents a hydrocarbon group or a hydrogen atom which may have a substituent. R ¹² represents —NHCOOR ¹³ (R ¹³ represents a hydrocarbon group which may have a substituent. A carbamate group or a thiazolyl group represented by
(3) The hydrophilic preservative is an isothiazoline compound represented by the following general formula (6), a nitro alcohol compound represented by the following general formula (7), a dithiol compound represented by the following general formula (8), It is at least one compound selected from the group consisting of a thiophene compound represented by the general formula (9) and a halocyanoacetamide compound represented by the following general formula (10), ) Or the industrial sterilizing composition according to (2),
General formula (6):

(In the formula, R ¹⁴ represents an optionally substituted hydrocarbon group having 1 to 3 carbon atoms or a hydrogen atom. R ¹⁵ and R ¹⁶ independently represent a hydrocarbon group (R ¹⁵ and Including the case where R ¹⁶ is ring-formed with a divalent hydrocarbon group.), Represents a halogen atom or a hydrogen atom.)
General formula (7):

(In the formula, R ¹⁷ represents a hydrocarbon group or a hydrogen atom. R ¹⁸ represents a hydrocarbon group, a halogen atom or a hydrogen atom having a hydroxyl group. R ¹⁹ represents a hydrocarbon group or a halogen having a hydroxyl group. Indicates an atom.)
General formula (8):

(In the formula, X ² and X ³ independently represent a halogen atom or a hydrogen atom.)
General formula (9):

(In the formula, R ²⁰ , R ²¹ , R ²² and R ²³ independently represent a hydrocarbon group, a halogen atom or a hydrogen atom which may have a substituent.)
General formula (10):

(In the formula, X ⁴ and X ⁵ independently represent a halogen atom or a hydrogen atom. R ²⁴ represents a hydrocarbon group which may have a substituent.)
(4) The industrial sterilizing composition according to any one of (1) to (3), which is an aqueous liquid agent.

  According to the industrial bactericidal composition of the present invention, by using the alkylimidazole compound represented by the general formula (1), a combination with a hydrophobic antifungal agent or a combination with a hydrophilic preservative In either case, it can be prepared as a homogeneous aqueous system. Therefore, a sufficient control effect against harmful microorganisms can be exhibited, and the amount of the organic solvent used can be reduced to reduce the burden on the environment.

  The industrial bactericidal composition of the present invention contains an alkylimidazole compound, a hydrophobic fungicide and / or a hydrophilic preservative, and water.

  The alkylimidazole compound used in the present invention is represented by the following general formula (1).

  General formula (1):

(In the formula, R ¹ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. R ² , R ³ and R ⁴ represent an optionally substituted carbon number. 1 to 18 hydrocarbon groups or hydrogen atoms.)
In the general formula (1), examples of the hydrocarbon group of the hydrocarbon group having 1 to 18 carbon atoms which may have a substituent represented by R ¹ , R ² , R ³ and R ⁴ include, for example, an alkyl group Alkenyl group, alkynyl group, cycloalkyl group, aryl group, aralkyl group and the like.

  Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, 2-methylpentyl, tert- 1-18 carbon atoms such as pentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. Of the alkyl group.

  Examples of the alkenyl group include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, C2-C18 alkenyl groups, such as octadecenyl, are mentioned.

  Examples of the alkynyl group include alkynyl groups having 2 to 18 carbon atoms such as ethynyl, 2-propynyl, butynyl, hexynyl, heptynyl, octynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl and the like. It is done.

  Examples of the cycloalkyl group include cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl.

  Examples of the aryl group include aryl groups having 6 to 18 carbon atoms such as phenyl, tolyl, xylyl, naphthyl, azulenyl, biphenyl and the like.

  Examples of the aralkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, diphenylmethyl, o, m or p-methylbenzyl, o, m or p-ethylbenzyl, o, m or p-isopropylbenzyl, o, m or p-tert-butylbenzyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylbenzyl, 2,3,4-, 3,4,5- or 2,4,6-trimethylbenzyl, 5-isopropyl-2-methylbenzyl, 2-isopropyl-5-methylbenzyl, 2- Methyl-5-tert-butylbenzyl, 2,4-, 2,5- or 3,5-diisopropylbenzyl, 3,5-di-tert-butylbenzyl, 1 (2-methylphenyl) ethyl, 1- (3-methylphenyl) ethyl, 1- (4-methylphenyl) ethyl, 1- (2-isopropylphenyl) ethyl, 1- (3-isopropylphenyl) ethyl, 1- (4-Isopropylphenyl) ethyl, 1- (2-tert-butylphenyl) ethyl, 1- (4-tert-butylphenyl) ethyl, 1- (2-isopropyl-4-methylphenyl) ethyl, 1- (4 -Isopropyl-2-methylphenyl) ethyl, 1- (2,4-dimethylphenyl) ethyl, 1- (2,5-dimethylphenyl) ethyl, 1- (3,5-dimethylphenyl) ethyl, 1- (3 , 5-di-tert-butylphenyl) ethyl and the like, and an aralkyl group having 7 to 18 carbon atoms.

Examples of the substituent of the hydrocarbon group having 1 to 18 carbon atoms which may have a substituent represented by R ¹ , R ² , R ³ and R ⁴ include a hydroxyl group and a halogen atom (for example, chlorine, Fluorine, bromine, iodine, etc.), cyano group, amino group, carboxyl group, alkoxy group (for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, C1-C6 alkoxy groups such as neopentyloxy and hexyloxy), aryloxy groups (such as phenoxy groups), alkoxycarbonyl groups (such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxy) Carbonyl, isobutoxy A C1-C6 alkoxycarbonyl group such as bonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, hexyloxycarbonyl, etc.), an alkylthio group (for example, methylthio, And alkylthio groups having 1 to 4 carbon atoms such as ethylthio, propylthio, and butylthio) and arylthio groups (eg, phenylthio group). These substituents may be the same or different and may be substituted by 1 to 5, preferably 1 to 3.

The hydrocarbon group having 1 to 18 carbon atoms which may have a substituent represented by R ¹ described above preferably has no substituent, and among them, an alkyl group is preferable. . Furthermore, this alkyl group preferably has 6 to 18 carbon atoms, more preferably 8 to 12 carbon atoms. Particularly preferred alkyl groups include dodecyl.

The hydrocarbon group having 1 to 18 carbon atoms which may have a substituent represented by R ² described above preferably has no substituent, and among them, an alkyl group is preferable. . Further, this alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. Particularly preferred alkyl groups include methyl.

The hydrocarbon group having 1 to 18 carbon atoms which may have a substituent represented by R ³ and R ⁴ described above preferably has no substituent, and among them, Alkyl groups are preferred. Further, this alkyl group preferably has 1 to 6 carbon atoms,
What is 1-3 is more preferable.

R ³ and R ⁴ are particularly preferably a hydrogen atom.

Preferred embodiments of general formula (1) include, for example, an embodiment in which R ¹ is an alkyl group having 6 to 18 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ are hydrogen atoms. It is done.

  The alkylimidazole compound represented by the general formula (1) can be produced by a known method according to the following specific compounds (for example, (i) JP-A-51-54925, (ii) ) S. Khabadidede et al., "Synthesis of N-alkylated of Imidazol as Antibiotic as Antibacterial Chemicals USA, Bioorganic, USA". , Vol. 13, pp. 2863-2865., (Iii) Hirofumi Shibata et al., “Antimicrobial activity of 2-alkylimidazole derivatives”, antibacterial and antifungal Society, 1984, Vol. 12, No. 8, pp.371-375. Reference). Specific examples thereof include 2-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1-propylimidazole, 2-isopropylimidazole, 1-butylimidazole, 1-pentylimidazole, 1-hexylimidazole, 1-hexyl-2-methylimidazole, 1-heptylimidazole, 1-octylimidazole, 1-octyl-2-methylimidazole, 1-octyl-2-ethylimidazole, 1-octyl-2-propylimidazole 1-nonylimidazole, 1-nonyl-2-methylimidazole, 1-decylimidazole, 1-decyl-2-methylimidazole, 1-undecylimidazole, 2-undecylimidazole, 1-dodecylimidazole 1-dodecyl-2-methylimidazole, 1-dodecyl-2-ethylimidazole, 1-dodecyl-2-propylimidazole, 1-tridecylimidazole, 1-tetradecylimidazole, 1-hexadecylimidazole, 2-heptadecylimidazole 1-octadecylimidazole, 1-benzyl-2-methylimidazole and the like. Of these, 1-dodecyl-2-methylimidazole is preferable. These alkylimidazole compounds may be used alone or in combination of two or more.

  The hydrophobic antifungal agents used in the present invention include isothiazoline compounds represented by the following general formulas (2) and (3), haloacetylene compounds represented by the following general formula (4), and the following general formula ( And at least one compound selected from the group consisting of benzimidazole compounds represented by 5).

  The isothiazoline-based compound as the hydrophobic antifungal agent used in the present invention is represented by the following general formula (2) and / or (3).

  General formula (2):

(In the formula, R ⁵ represents an optionally substituted hydrocarbon group having 6 to 12 carbon atoms. R ⁶ and R ⁷ are independently a hydrocarbon group (R ⁶ and R ⁷ are Including a case where a ring is formed by a divalent hydrocarbon group.), A halogen atom or a hydrogen atom.)
General formula (3):

(In the formula, R ⁸ represents a hydrocarbon group or a hydrogen atom which may have a substituent. The A ring represents a benzene ring which may have a substituent.)
In the general formula (2), examples of the hydrocarbon group having 6 to 12 carbon atoms which may have a substituent represented by R ⁵ include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group. Groups, aryl groups, aralkyl groups, etc., specifically, among the hydrocarbon groups having 1 to 18 carbon atoms which may have the above-described substituents, those having 6 to 12 carbon atoms are mentioned. It is done. Among these, a C6-C12 hydrocarbon group which does not have a substituent is preferable, and a C6-C12 alkyl group is more preferable. Particularly preferred is n-octyl.

In the general formula (2), examples of the hydrocarbon group represented by R ⁶ and R ⁷ include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like. The number of carbon atoms is not limited, and examples thereof include the same as the above-described hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. Among these, a C1-C6 hydrocarbon group which does not have a substituent is preferable, and especially a C1-C6 alkyl group which does not have a substituent is preferable.

Examples of the divalent hydrocarbon group when R ⁶ and R ⁷ are ring-formed with a divalent hydrocarbon group include methylene, ethylene, trimethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene C1-C6 alkylene groups, such as these, are mentioned.

Examples of the halogen atom represented by R ⁶ and R ⁷ include fluorine, chlorine, bromine and iodine, and preferably chlorine.

R ⁶ and R ⁷ are particularly preferably a halogen atom or a hydrogen atom, and more preferably a hydrogen atom.

As a preferred embodiment of the general formula (2), for example, ^{R 5} may be mentioned a mode alkyl group having 6 to 12 carbon atoms, ^{R 6} and ^{R 7} is a halogen atom or a hydrogen atom.

In the general formula (3), examples of the hydrocarbon group which may have a substituent represented by R ⁸ include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Specific examples of the hydrocarbon group include, but are not limited to, the carbon number, and the same as the above-described hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. Among them, a hydrocarbon group having 1 to 6 carbon atoms which does not have a substituent is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and n-butyl is particularly preferable.

Examples of the substituent of the benzene ring which may have a substituent represented by A include a hydrocarbon group which may have a substituent represented by R ¹ , R ² , R ³ and R ⁴ The same thing is mentioned. Preferably, a halogen atom and an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.) can be used. These substituents are the same or different and may be substituted by 1 to 4, preferably 1 or 2. As a preferred embodiment of the benzene ring which may have a substituent represented by A ring, a benzene ring having no substituent can be mentioned.

As a preferable aspect of General formula (3), the aspect whose R < ⁸ > is a C1-C6 alkyl group which does not have a substituent, and ring A is a benzene ring which does not have a substituent is mentioned, for example. Include an embodiment in which R ⁸ is n-butyl or a hydrogen atom, and ring A is benzene.

  The hydrophobic isothiazoline compounds represented by the general formulas (2) and (3) can be produced by known methods according to the following specific compounds. Specific examples thereof include, for example, 2- n-octyl-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-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, Nn -Butyl-1,2-benzisothiazolin-3-one and the like. Of these, preferably 2-n-octyl-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, 1,2-benzisothiazolin-3-one, Nn-butyl-1,2-benzisothiazoline -3-one is mentioned. Of these, 2-n-octyl-4-isothiazolin-3-one is more preferable. These isothiazoline compounds may be used alone or in combination of two or more.

  The haloacetylene compound used in the present invention is represented by the following general formula (4).

  General formula (4):

(In the formula, R ⁹ and R ¹⁰ independently represent a hydrocarbon group or a hydrogen atom which may have a substituent. X ¹ represents a halogen atom. M represents an integer of 0 or 1. .)
In the general formula (4), examples of the hydrocarbon group which may have a substituent represented by R ⁹ and R ¹⁰ include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group. Groups, aralkyl groups, and the like. Specifically, the carbon number is not limited, but the same as the above-described hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. Can be mentioned. Among these, a hydrocarbon group having no substituent is preferable, and an alkyl group having no substituent is particularly preferable. As the alkyl group, preferably, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, sec-pentyl, t-pentyl, hexyl, heptyl, C1-C10 alkyl groups, such as n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, are mentioned, More preferably, n-butyl is mentioned.

In the general formula (4), examples of the halogen atom represented by X ¹ include fluorine, chlorine, bromine and iodine, and preferably iodine.

As a preferable embodiment of the general formula (4), for example, R ⁹ and R ¹⁰ are both hydrogen atoms, one of R ⁹ and R ¹⁰ is a hydrogen atom, and the other is an alkyl group having 1 to 10 carbon atoms, or An embodiment in which R ⁹ and R ¹⁰ are both an alkyl group having 1 to 10 carbon atoms, X ¹ is iodine, and m is 1 is exemplified. More preferably, one of R ⁹ and R ¹⁰ is a hydrogen atom, the other is an alkyl group having 1 to 10 carbon atoms, X ¹ is iodine, and m is 1. Particularly preferred is an embodiment in which any one of R ⁹ and R ¹⁰ is a hydrogen atom, the other is n-butyl, X ¹ is iodine, and m is 1.

  The haloacetylene compound represented by the general formula (4) can be produced by a known method according to the following specific compounds. Specific examples thereof include haloacetylene compounds when m is 0. As certain acid amide derivatives, for example, 3-chloropropiolic acid amide, N-methyl-3-chloropropiolic acid amide, N-ethyl-3-chloropropiolic acid amide, N-propyl-3-chloropropiolic acid Amides, N-butyl-3-chloropropiolic acid amides, N-hexyl-3-chloropropiolic acid amides, N-octyl-3-chloropropiolic acid amides, N-cyclohexyl-3-chloropropiolic acid amides, etc. (N-substituted-) 3-chloropropiolic amides such as 3-bromopropiolic amide, N-methyl-3-but Mopropiolic acid amide, N-ethyl-3-bromopropiolic acid amide, N-propyl-3-bromopropiolic acid amide, N-butyl-3-bromopropiolic acid amide, N-hexyl-3-bromopropiolic acid (N-substituted-) 3-bromopropiolic amides, such as 3-iodopropiolic amides, such as amides, N-octyl-3-bromopropiolic amides, N-cyclohexyl-3-bromopropiolic amides N-methyl-3-iodopropiolic amide, N-ethyl-3-iodopropiolic amide, N-propyl-3-iodopropiolic amide, N-butyl-3-iodopropiolic amide, N -Hexyl-3-iodopropiolic amide, N-octyl-3-iodopropiolic amide, N (N- substituted -), such as cyclohexyl-3-iodo-prop-ol acid amides such as 3-iodo propiolaldehyde acid amide. Preferably, (N-substituted-) 3-iodopropiolic acid amide is mentioned, More preferably, N-butyl-3-iodopropiolic acid amide is mentioned.

  Examples of the carbamate derivative that is a haloacetylene compound when m is 1, for example, 3-iodo-2-propynylmethyl carbamate, 3-iodo-2-propynylethyl carbamate, 3-iodo-2-propynylpropyl carbamate, 3-iodo-2-propynyl alkyl carbamates such as 3-iodo-2-propynyl butyl carbamate, 3-iodo-2-propynyl hexyl carbamate, 3-iodo-2-propynyl octyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate Etc. Of these, 3-iodo-2-propynylbutyl carbamate is preferable. These haloacetylene compounds may be used alone or in combination of two or more.

  The benzimidazole compound used in the present invention is represented by the following general formula (5).

  General formula (5):

(In the formula, R ¹¹ represents a hydrocarbon group or a hydrogen atom which may have a substituent. R ¹² represents —NHCOOR ¹³ (R ¹³ represents a hydrocarbon group which may have a substituent. A carbamate group or a thiazolyl group represented by
In the general formula (5), the hydrocarbon group which may have a substituent represented by R ¹¹ includes the hydrocarbon group which may have a substituent represented by R ⁹ and R ¹⁰ described above. The same thing is mentioned. Among these, a hydrocarbon group having no substituent is preferable, and an alkyl group having no substituent is particularly preferable. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, etc., and methyl is particularly preferable. .

As an embodiment in the case where R ¹¹ is a hydrocarbon group which may have a substituent, any of the 4-position, 5-position, 6-position and 7-position of the benzimidazole ring has a substituent. The aspect substituted by a good hydrocarbon group is mentioned. In the case where R ¹¹ is a hydrogen atom, the 4-position, 5-position, 6-position and 7-position of the benzimidazole ring are not substituted with a hydrocarbon group having no substituent. An embodiment, that is, an embodiment in which R ¹¹ is deleted in the general formula (5) can be mentioned. The most preferred embodiments of R ^11, a hydrogen atom, in the general formula (5) is an aspect which R ¹¹ is deleted.

In —NHCOOR ¹³ (carbamate group) represented by R ¹² , the hydrocarbon group optionally having a substituent represented by R ¹³ has the substituent represented by R ⁹ and R ¹⁰ described above. The thing similar to the hydrocarbon group which may be mentioned is mentioned. Among these, a hydrocarbon group having no substituent is preferable, and an alkyl group having no substituent is particularly preferable. As the alkyl group, preferably, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, etc. is mentioned. Is preferred.

Examples of the thiazolyl group represented by R ¹² include 2-thiazolyl, 4-thiazolyl, 5-thiazolyl and the like. Preferably, 4-thiazolyl is used.

The benzimidazole compound represented by the general formula (5) can be produced by a known method according to the following specific compounds. Specific examples thereof include carbamates in which R ¹² is represented by —NHCOOR ^13. When it is a group, examples thereof include methyl 2-benzimidazole carbamate and ethyl 2-benzimidazole carbamate. Moreover, when R < ¹¹ > is a thiazolyl group, 2- (4-thiazolyl) benzimidazole etc. are mentioned, for example. Among these, Preferably, methyl 2-benzimidazole carbamate is mentioned. These benzimidazole compounds may be used alone or in combination of two or more.

  Examples of the hydrophilic preservative used in the present invention include an isothiazoline compound represented by the following general formula (6), a nitroalcohol compound represented by the following general formula (7), and a dithiol compound represented by the following general formula (8). And at least one compound selected from the group consisting of a compound, a thiophene compound represented by the following general formula (9), and a halocyanoacetamide compound represented by the following general formula (10).

  The isothiazoline-based compound as the hydrophilic preservative used in the present invention is represented by the following general formula (6).

  General formula (6):

(In the formula, R ¹⁴ represents an optionally substituted hydrocarbon group having 1 to 3 carbon atoms or a hydrogen atom. R ¹⁵ and R ¹⁶ independently represent a hydrocarbon group (R ¹⁵ and Including the case where R ¹⁶ is ring-formed with a divalent hydrocarbon group.), Represents a halogen atom or a hydrogen atom.)
In the general formula (6), examples of the hydrocarbon group having 1 to 3 carbon atoms which may have a substituent represented by R ¹⁴ include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group. Specifically, among the hydrocarbon groups having 1 to 18 carbon atoms which may have the above-described substituent, those having 1 to 3 carbon atoms are exemplified. Among these, a hydrocarbon group having no substituent is preferable, an alkyl group is more preferable, and methyl is particularly preferable.

In the general formula (6), examples of the hydrocarbon group represented by R ¹⁵ and R ¹⁶ include the same hydrocarbon groups as those represented by R ⁶ and R ⁷ described above. Among these, a C1-C3 hydrocarbon group which does not have a substituent is preferable, and a C1-C3 alkyl group is especially preferable.

As the divalent hydrocarbon group when R ¹⁵ and R ¹⁶ are ring-formed with a divalent hydrocarbon group, the same divalent hydrocarbon groups as those described above for R ⁶ and R ⁷ can be used. Can be mentioned.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably chlorine.

R ¹⁵ and R ¹⁶ are particularly preferably a halogen atom or a hydrogen atom, and more preferably a hydrogen atom.

As a preferred embodiment of the general formula (6), for example, R ¹⁴ is an alkyl group having 1 to 3 carbon atoms, R ¹⁵ and R ¹⁶ can be mentioned a mode is a halogen atom or a hydrogen atom.

  The hydrophilic isothiazoline compound represented by the general formula (6) can be produced by a known method according to the following specific compounds. Specific examples thereof include, for example, 2-methyl-4- Isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, Examples include 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 1,2-benzisothiazolin-3-one. Of these, preferably 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazoline-3 -One, 1,2-benzisothiazolin-3-one. Of these, 2-methyl-4-isothiazolin-3-one is more preferable. These isothiazoline compounds may be used alone or in combination of two or more.

  The nitro alcohol compound used in the present invention is represented by the following general formula (7).

  General formula (7):

(In the formula, R ¹⁷ represents a hydrocarbon group or a hydrogen atom. R ¹⁸ represents a hydrocarbon group, a halogen atom or a hydrogen atom having a hydroxyl group. R ¹⁹ represents a hydrocarbon group or a halogen having a hydroxyl group. Indicates an atom.)
In the general formula (7), examples of the hydrocarbon group represented by R ¹⁷ include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like. Although not limited, the thing similar to a C1-C18 hydrocarbon group which may have the above-mentioned substituent is mentioned. Among these, a hydrocarbon group having no substituent is preferable, and an alkyl group is more preferable. As an alkyl group, Preferably, C1-C4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, are mentioned.

In the general formula (7), examples of the hydrocarbon group having a hydroxyl group represented by R ¹⁸ and R ¹⁹ include the same hydrocarbon groups as those described above for R ¹⁷ . It is an alkyl group. As an alkyl group, Preferably, C1-C4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, are mentioned. In addition, for example, 1 to 3 hydroxyl groups are preferably substituted on a hydrocarbon group, and one of them is preferably substituted.

  As such a hydrocarbon group having a hydroxyl group, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl and the like are preferable, and hydroxymethyl is more preferable.

In the general formula (7), examples of the halogen atom represented by R ¹⁸ and R ¹⁹ include fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.

As a preferred embodiment of the general formula (7), for example, R ¹⁷ is an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, R ¹⁸ is an alkyl group having 1 to 4 carbon atoms having a hydroxyl group, a bromine atom , A chlorine atom or a hydrogen atom, and R ¹⁹ is an alkyl group having 1 to 4 carbon atoms having a hydroxyl group, a bromine atom or a chlorine atom, more preferably, R ¹⁷ is a methyl or hydrogen atom. And R ¹⁸ is hydroxylethyl, hydroxymethyl, bromine atom or hydrogen atom, and R ¹⁹ is hydroxylmethyl, bromine atom or chlorine atom.

  The nitroalcohol compound represented by the general formula (7) can be produced by a known method according to the following specific compounds. Specific examples thereof include, for example, 2-bromo-2-nitropropane. -1,3-diol, 2-bromo-2-nitrobutane-1,3-diol, 3-bromo-3-nitropentane-2,4-diol, 2,2-dibromo-2-nitro-1-ethanol, 2-nitro-1,3-propanediol, tris (hydroxymethyl) nitromethane, 3,3-dibromo-3-nitro-2-propanol, 2-chloro-2-nitroethanol, 2-chloro-2-nitro-1 , 3-propanediol, 3-chloro-3-nitro-2-propanol and the like. Of these, Preferably, 2-bromo-2-nitropropane-1,3-diol and 2,2-dibromo-2-nitro-1-ethanol are used. These nitroalcohol compounds may be used alone or in combination of two or more.

  The dithiol compound used in the present invention is represented by the following general formula (8).

  General formula (8):

(In the formula, X ² and X ³ independently represent a halogen atom or a hydrogen atom.)
In the general formula (8), examples of the halogen atom represented by X ² and X ³ include fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.

As a preferred embodiment of the general formula (8), for example, X ² and X ³ are both bromine atoms, X ² and X ³ are both chlorine atoms, and X ² and X ³ are either bromine atoms and the other is An embodiment in which any one of a chlorine atom, X ² and X ³ is a bromine atom and the other is a hydrogen atom, and one of X ² and X ³ is a chlorine atom and the other is a hydrogen atom is exemplified.

  The dithiol compound represented by the following general formula (8) can be produced by a known method according to the following specific compounds. Specific examples thereof include, for example, 4,5-dichloro-1, 2-dithiol-3-one, 4,5-dibromo-1,2-dithiol-3-one, 4-chloro-1,2-dithiol-3-one, 4-bromo-1,2-dithiol-3-one ON etc. are mentioned. Of these, 4,5-dibromo-1,2-dithiol-3-one is preferable. These dithiol compounds may be used alone or in combination of two or more.

  The thiophene compound used in the present invention is represented by the following general formula (9).

  General formula (9):

(In the formula, R ²⁰ , R ²¹ , R ²² and R ²³ independently represent a hydrocarbon group, a halogen atom or a hydrogen atom which may have a substituent.)
In the general formula (9), the hydrocarbon group which may have a substituent represented by R ²⁰ , R ²¹ , R ²² and R ²³ has the substituent represented by R ⁹ and R ¹⁰ described above. The thing similar to the hydrocarbon group which may be mentioned is mentioned. Among these, a hydrocarbon group having no substituent is preferable, and an alkyl group having no substituent is particularly preferable. As an alkyl group, Preferably, C1-C4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, are mentioned.

Examples of the halogen atom represented by R ²⁰ , R ²¹ , R ²² and R ²³ include fluorine, chlorine, bromine and iodine, preferably chlorine.

In a preferred embodiment of the general formula (9), R ²⁰ , R ²¹ , R ²² and R ²³ are all halogen atoms, R ²⁰ , R ²¹ and R ²² are halogen atoms, R ²³ is a hydrogen atom, R ²⁰ and An embodiment in which R ²¹ is a halogen atom and R ²² and R ²³ are hydrogen atoms is exemplified. Among these, preferred is an embodiment in which all of R ²⁰ , R ²¹ , R ²² and R ²³ are halogen atoms, and in particular, all of R ²⁰ , R ²¹ , R ²² and R ²³ are chlorine atoms.

  The thiophene compound represented by the general formula (9) can be produced by a known method according to the following specific compounds, and specific examples thereof include, for example, 3,3,4,4-tetra Chlorotetrahydrothiophene-1,1-dioxide, 3,3,4,4-tetrabromotetrahydrothiophene-1,1-dioxide, 3,4-dichlorotetrahydrothiophene-1,1-dioxide, 3,3,4-trichloro Examples thereof include tetrahydrothiophene-1,1-dioxide, 3,3,4-tribromotetrahydrothiophene-1,1-dioxide and the like. Of these, 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide are preferable. These thiophene compounds may be used alone or in combination of two or more.

  The halocyanoacetamide compound used in the present invention is represented by the following general formula (10).

  General formula (10):

(In the formula, X ⁴ and X ⁵ independently represent a halogen atom or a hydrogen atom. R ²⁴ represents a hydrocarbon group which may have a substituent.)
In the general formula (10), examples of the halogen atom represented by X ⁴ and X ⁵ include fluorine, chlorine, bromine, and iodine, and preferably bromine.

In the general formula (10), the hydrocarbon group which may have a substituent represented by R ²⁴ is the same as the hydrocarbon group which may have a substituent represented by R ⁹ and R ¹⁰ described above. Can be mentioned. Among these, a hydrocarbon group having no substituent is preferable, and an alkyl group having no substituent is particularly preferable. As an alkyl group, Preferably, C1-C4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, are mentioned.

  The halocyanoacetamide-based compound represented by the general formula (10) can be produced by a known method according to the following specific compounds. Specific examples thereof include, for example, monochlororocyanoacetamide, monobromo Examples include cyanoacetamide, dichlorocyanoacetamide, dibromocyanoacetamide, monochloromonobromocyanoacetamide, N-methyldibromocyanoacetamide, and preferably dibromocyanoacetamide. These halocyanoacetamide compounds may be used alone or in combination of two or more.

  The blending ratio of the alkylimidazole compound represented by the general formula (1) and the hydrophobic antifungal agent and / or the hydrophilic preservative is not particularly limited, but is 100 parts by weight of the alkylimidazole compound. The hydrophobic fungicide and / or hydrophilic preservative is 5 to 2000 parts by weight, preferably 10 to 1000 parts by weight.

  More specifically, with respect to 100 parts by weight of the imidazole compound represented by the general formula (1), the isothiazoline compound represented by the general formulas (2) and (3) is preferably 5 to 2000 parts by weight, Is 10 to 1000 parts by weight, and the haloacetylene compound represented by the general formula (4) is 5 to 2000 parts by weight, preferably 10 to 1000 parts by weight, and is represented by the general formula (5). The benzimidazole compound is 5 to 2000 parts by weight, preferably 10 to 1000 parts by weight, and the isothiazoline compound represented by the general formula (6) is 5 to 2000 parts by weight, preferably 10 to 1000 parts by weight. The nitroalcohol compound represented by the general formula (7) is 5 to 2000 parts by weight, preferably 10 to 1000 parts by weight. The dithiol compound represented by the general formula (8) is 5 to 2000 parts by weight, preferably 10 to 1000 parts by weight, and the thiophene compound represented by the general formula (9) is 5 to 2000 parts by weight. The amount is preferably 10 to 1000 parts by weight, and the halocyanoacetamide compound represented by the general formula (10) is 5 to 2000 parts by weight, preferably 10 to 1000 parts by weight.

  And the industrial disinfection composition of this invention is prepared so that pH value when diluted with water may become smaller than the pH value of the alkylimidazole type compound shown by the said General formula (1). By adjusting the pH value in this way, the alkylimidazole compound represented by the general formula (1) can be solubilized together with other active ingredients.

  The alkyl imidazole compound represented by the general formula (1) has a pH value of about 9 to 11 when blended in water. Therefore, in the preparation of the industrial sterilizing composition of the present invention, the pH value when a hydrophobic antifungal agent and / or a hydrophilic preservative is further blended is smaller than the pH value when these are not blended. Thus, for example, an acid is blended, and the pH is adjusted to 1 to 8, preferably 2 to 8.

  The acid is not particularly limited, and a known inorganic acid or organic acid can be used. Specific examples include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, and organic acids such as acetic acid and oxalic acid. The amount of the acid is appropriately determined.

  The industrial bactericidal composition of the present invention may be formulated according to the purpose and application, and its dosage form is not particularly limited. For example, it can be prepared as a liquid, preferably an aqueous liquid. In order to prepare an aqueous solution, for example, the above-described components and water are blended and mixed, as described above, so that the pH of the solution is smaller than the pH of the alkylimidazole compound. What is necessary is just to add an acid.

  Moreover, after mix | blending and mixing each above-mentioned component and water, it is made to adsorb | suck to an inorganic support | carrier, for example, may be granulated or pulverized, and also may be microencapsulated.

  In addition, as a solvent, alcohols and glycols soluble in water may be used together with water as long as the effects of the present invention are not impaired.

  Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, tert-butyl alcohol, and the like.

  Examples of glycols include methylene glycol, ethylene glycol, diethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether.

  When the industrial bactericidal composition of the present invention is used as a liquid agent, the blending ratio of the alkylimidazole compound represented by the general formula (1) and the hydrophobic antifungal agent and / or the hydrophilic preservative is particularly limited. The total amount of the alkylimidazole compound and the hydrophobic antifungal agent and / or the hydrophilic preservative is, for example, 0.5 to 50% by weight, preferably 1 to Prepare to be 30% by weight.

  Furthermore, the industrial sterilizing composition of the present invention may be a known antibacterial agent, antifungal agent, antialgae agent, antioxidant, light stabilizer, etc. other than those exemplified above depending on the purpose and application. You may add an additive suitably in the range which does not inhibit the effect of the industrial disinfection composition of this invention.

  Examples of other antiseptics, fungicides and anti-algae agents include phthalimide compounds, haloalkylthio compounds, pyrithione compounds, phenylurea compounds, triazine compounds, guanidine compounds, triazole compounds, quaternary ammonium Salt compounds, bis-quaternary ammonium salt compounds, organic iodine compounds, thiocarbamate compounds, nitrile compounds, pizirine compounds, benzothiazole compounds, oxathiazine compounds, cyanoacetamide compounds, thiocyanate compounds, etc. It is done.

  Examples of the phthalimide compound include N-1,1,2,2-tetrachloroethylthio-tetrahydrophthalimide (Captafol), N-trichloromethylthio-tetrahydrophthalimide (Captan), N-dichlorofluoromethylthiophthalimide (Fluorolpet), N- And trichloromethylthiophthalimide (Folpet).

  Examples of the haloalkylthio compounds include N-dimethylaminosulfonyl-N-tolyl-dichlorofluoromethanesulfamide (Tolylfluoride), N-dimethylaminosulfonyl-N-phenyl-dichlorofluoromethanesulfamide (Dichlofluoride) and the like. Can be mentioned.

  Examples of the pyrithione compound include sodium pyrithione and zinc pyrithione.

  Examples of the phenylurea compound include 3- (3,4-dichlorophenyl) -1,1-dimethylurea.

  Examples of the triazine compound include 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine.

  Examples of the guanidine compound include 1,6-di- (4'-chlorophenyldiguanide) -hexane, polyhexamethylene biguanidine hydrochloride, and the like.

  Examples of triazole compounds include α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (common name: tebuconazole). ), 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole (common name: propico) Nazole), 1-[[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole (common name: azaconazole), α- (4 -Chlorophenyl) -α- (1-cyclopropylethyl) -1H-1,2,4-triazole-1-ethanol (common name: cyproconazole) and the like.

  Examples of the quaternary ammonium salt compound include hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, benzalkonium chloride, di-n-decyl-dimethylammonium chloride, 1-hexadecylpyridinium chloride and the like.

  Examples of the bis-quaternary ammonium salt compound include N, N′-hexamethylene bis (4-carbamoyl-1-decylpyridinium bromide) and N, N′-hexamethylene bis (4-carbamoyl-1-decylpyridinium acetate). ), 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide), 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium acetate), and the like.

  Examples of the organic iodine compound include diiodomethyl-p-toluylsulfone, p-chlorophenyl-3-iodopropargyl formal, and the like.

  Examples of the thiocarbamate compound include tetramethylthiuram disulfide.

  Examples of the nitrile compound include 2,4,5,6-tetrachloroisophthalonitrile.

  Examples of the pyridine compound include 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine.

  Examples of the benzothiazole compound include 2- (4-thiocyanomethylthio) benzothiazole.

  Examples of the oxathiazine compound include 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide.

  Examples include cyanoacetamide compounds such as 2,2-dibromo-3-nitrilopropanamide.

  Examples of the thiocyanate compounds include methylene bis thiocyanate.

    In the industrial sterilizing composition of the present invention, a known buffering agent can be blended from the viewpoint of stabilizing the pH value when diluted with water.

  And the industrial bactericidal composition of this invention prepared in this way is shown with the combination of the alkylimidazole type compound shown by the said General formula (1), and a hydrophobic antifungal agent, and the said General formula (1). In any case of a combination of an alkylimidazole compound and a hydrophilic preservative, it can be prepared as a uniform aqueous system. In addition, a synergistic effect due to sufficient antifungal performance and antiseptic performance against harmful microorganisms can be exhibited, and the amount of organic solvent used can be reduced to reduce the burden on the environment.

  In addition, the industrial sterilizing composition of the present invention may be appropriately determined depending on the application target, and is, for example, 5 to 1000 mg (active ingredient) / kg (product), preferably 10 to 500 mg ( Used as concentration of active ingredient) / kg (product).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the symbol of the component used for a following example and a comparative example is shown below.
SZ: 1-dodecyl-2-methylimidazole OIT: 2-n-octyl-4-isothiazolin-3-one H-MIT: 2-methyl-4-isothiazolin-3-one Example 1
SZ5.0g, OIT5.0g, water 88.3g, and 36% hydrochloric acid 1.7g were mix | blended, and the aqueous liquid agent was obtained by stirring and mixing.

Example 2
SZ1.0g, OIT10.0g, water 88.4g, and 36% hydrochloric acid 0.6g were mix | blended, and the aqueous liquid agent was obtained by stirring and mixing.

Comparative Example 1
An aqueous liquid agent was obtained by blending 5.0 g of OIT and 95.0 g of water.

Comparative Example 2
OIT 5.0g, water 95.0g, and 36% hydrochloric acid 1.7g were mixed and stirred to obtain an aqueous liquid.

Evaluation Regarding the aqueous solutions obtained in Examples 1 and 2 and Comparative Example 1, the pH (layer separation occurred (in this case, the pH of the aqueous layer) was measured, and the appearance was visually observed. Are shown in Table 1. Moreover, what mix | blended SZ with water independently is shown as a control.

Example 3
An aqueous solution was obtained by mixing 5.0 g of SZ, 10.0 g of an aqueous solution containing 50% of H-MIT, 84.3 g of water, and 0.7 g of 36% hydrochloric acid, and stirring and mixing them. This aqueous solution was a transparent solution having a pH of 5.3.

Test example 1
The antiseptic performance and antifungal performance were evaluated by the following antiseptic effect test and antifungal effect test, using the following aqueous solution prepared by blending SZ and OIT in water.
(I) An aqueous solution (pH 5.7) prepared by mixing 10.0 g of SZ, 88.0 g of water, and 2.0 g of 36% hydrochloric acid and stirring and mixing them.
(Ii) An aqueous liquid (pH 5.5) obtained by mixing SZ 7.5 g, OIT 2.5 g, water 88.1 g, and 36% hydrochloric acid 1.9 g and stirring and mixing them.
(Iii) An aqueous solution (pH 5.4) prepared by mixing SZ 5.0 g, OIT 5.0 g, water 88.3 g, and 36% hydrochloric acid 1.7 g and stirring and mixing them.
(Iv) An aqueous solution (pH 1.2) obtained by mixing 2.5 g of SZ, 7.5 g of OIT, 88.5 g of water, and 1.5 g of 36% hydrochloric acid, and stirring and mixing them.
(V) An aqueous solution (pH 1.2) obtained by mixing 10.0 g of OIT, 89.6 g of water, and 0.4 g of 36% hydrochloric acid and stirring them.

  The test was a multiple dilution method using a glucose-bouillon agar medium adjusted to pH 6, using the test bacteria shown in Table 2, the bacteria were cultured at 33 ° C. for 18 hours, and the fungi and yeast at 33 ° C. After culturing for 18 hours, the cells were cultured at 28 ° C. for 2 days, and the minimum inhibitory concentration (MIC: μg / ml) of each was determined. The results are shown in Table 2.

Test example 2
The antiseptic performance and fungicidal performance were evaluated in the same manner as in Test Example 1 except that the following aqueous liquid composition prepared by blending SZ and H-MIT in water was used. The results are shown in Table 3.
(I) An aqueous solution (pH 5.7) obtained by mixing 10.0 g of SZ, 88.0 g of water, and 2.0 g of 36% hydrochloric acid and stirring them.
(Ii) SZ 7.5 g, 5.0 g of an aqueous solution containing 50% of H-MIT (2.5 g of H-MIT content), 85.6 g of water, and 1.9 g of 36% hydrochloric acid were mixed with stirring. An aqueous solution (pH 5.6).
(Iii) SZ5.0 g, 10.0 g of an aqueous solution containing 50% of H-MIT (5.0 g of H-MIT content), 84.3 g of water, and 0.7 g of 36% hydrochloric acid were mixed and stirred. An aqueous solution (pH 5.3).
(Iv) 2.5 g of SZ, 15.0 g of an aqueous solution containing 50% of H-MIT (7.5 g of H-MIT), 82.0 g of water, and 0.5 g of 36% hydrochloric acid were mixed with stirring. An aqueous solution (pH 5.0).
(V) An aqueous liquid (pH 4.5) prepared by mixing and stirring 20.0 g of an aqueous solution containing 50% H-MIT (10 g of H-MIT content) and 80 g of water.

Claims (4)

An alkylimidazole compound represented by the following general formula (1), a hydrophobic fungicide and / or a hydrophilic preservative,
An industrial bactericidal composition, wherein the pH value when diluted with water is smaller than the pH value of the alkylimidazole compound.
General formula (1):

(In the formula, R ¹ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. R ² , R ³ and R ⁴ independently have a substituent. A C1-C18 hydrocarbon group or a hydrogen atom may be used.) Hydrophobic fungicides are isothiazoline compounds represented by the following general formulas (2) and (3), haloacetylene compounds represented by the following general formula (4), and benzs represented by the following general formula (5) The industrial sterilization composition according to claim 1, wherein the composition is at least one compound selected from the group consisting of imidazole compounds.
General formula (2):

(In the formula, R ⁵ represents an optionally substituted hydrocarbon group having 6 to 12 carbon atoms. R ⁶ and R ⁷ are independently a hydrocarbon group (R ⁶ and R ⁷ are Including a case where a ring is formed by a divalent hydrocarbon group.), A halogen atom or a hydrogen atom.)
General formula (3):

(In the formula, R ⁸ represents a hydrocarbon group or a hydrogen atom which may have a substituent. The A ring represents a benzene ring which may have a substituent.)
General formula (4):

(In the formula, R ⁹ and R ¹⁰ independently represent a hydrocarbon group or a hydrogen atom which may have a substituent. X ¹ represents a halogen atom. M represents an integer of 0 or 1. .)
General formula (5):

(In the formula, R ¹¹ represents a hydrocarbon group or a hydrogen atom which may have a substituent. R ¹² represents —NHCOOR ¹³ (R ¹³ represents a hydrocarbon group which may have a substituent. A carbamate group or a thiazolyl group represented by The hydrophilic preservative is an isothiazoline compound represented by the following general formula (6), a nitro alcohol compound represented by the following general formula (7), a dithiol compound represented by the following general formula (8), the following general formula ( The thiophene compound represented by 9) and at least one compound selected from the group consisting of halocyanoacetamide compounds represented by the following general formula (10): The industrial sterilizing composition as described.
General formula (6):

(In the formula, R ¹⁴ represents an optionally substituted hydrocarbon group having 1 to 3 carbon atoms or a hydrogen atom. R ¹⁵ and R ¹⁶ independently represent a hydrocarbon group (R ¹⁵ and Including the case where R ¹⁶ is ring-formed with a divalent hydrocarbon group.), Represents a halogen atom or a hydrogen atom.)
General formula (7):

(In the formula, R ¹⁷ represents a hydrocarbon group or a hydrogen atom. R ¹⁸ represents a hydrocarbon group, a halogen atom or a hydrogen atom having a hydroxyl group. R ¹⁹ represents a hydrocarbon group or a halogen having a hydroxyl group. Indicates an atom.)
General formula (8):

(In the formula, X ² and X ³ independently represent a halogen atom or a hydrogen atom.)
General formula (9):

(In the formula, R ²⁰ , R ²¹ , R ²² and R ²³ independently represent a hydrocarbon group, a halogen atom or a hydrogen atom which may have a substituent.)
General formula (10):

(In the formula, X ⁴ and X ⁵ independently represent a halogen atom or a hydrogen atom. R ²⁴ represents a hydrocarbon group which may have a substituent.)   The industrial sterilizing composition according to any one of claims 1 to 3, wherein the composition is an aqueous liquid agent.