JP4502709B2 - Disinfectant composition and stabilization method - Google Patents

Description

  The present invention relates to a bactericide composition comprising an alkylimidazole compound and an active ingredient having antimicrobial activity, wherein the stability of the alkylimidazole compound is improved, and a method for stabilizing the alkylimidazole compound.

  Water used in the papermaking process in the pulp and paper industry, water used as circulating cooling water, and aqueous compositions (for example, aqueous emulsions, coating agents such as aqueous paints, cutting oils, printing pastes, etc.), microorganisms propagate and work environment There is a risk of deteriorating the productivity and reducing the productivity and quality. For this reason, various preservatives and antibacterial agents are used, but in these applications, the antibacterial agents are required to be stable over a long period of time.

  Japanese Patent Application Laid-Open No. 5-286815 (Patent Document 1) discloses an industrial disinfectant containing an isothiazolone compound, an alkali metal salt of bromic acid or iodic acid, and water. This document includes 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline under the condition that water coexists by adding an alkali metal salt of bromic acid or iodic acid. A method for stabilizing an isothiazolone-based compound such as -3-one is also disclosed. Further, it is also described that a water-soluble glycol solvent is contained, and ethylene glycol is used in the examples. JP-A-9-263504 (Patent Document 2) contains a composition containing an isothiazolone compound, an alkali metal salt of bromic acid or iodic acid, and water, and having a pH adjusted to 3.5 to 4.5. It is disclosed. This document also describes that a water-soluble glycol solvent may be included, and that the stability of the isothiazolone compound can be improved by adjusting the pH to the above range.

  JP-A-9-124625 (Patent Document 3) discloses 2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one or a mixture thereof, iodic acid, and periodic acid. Or a salt thereof, 5-chloro-2-methyl-4-isothiazolin-3-one, and a composition having a pH of 8.5 or more is disclosed. In this document, 2-methyl is added under severe conditions (for example, in the form of a metal working fluid containing cutting oil) having a pH of 8.5 or more by adding the iodic acid, periodic acid or a salt thereof. It is also disclosed that -4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one or mixtures thereof can be stabilized.

  On the other hand, alkylimidazole compounds are also known as antibacterial compounds. For example, Japanese Patent Application Laid-Open No. 51-54925 (Patent Document 4) discloses a bactericide preparation containing an alkylimidazole compound together with an ordinary regulator. In this document, alkyl imidazole compounds such as 1-dodecyl-2-methylimidazole are described in S.P. Aureus, C.I. Albicans, H.M. Anomala, T. It is described that it exhibits a bactericidal action against strains such as Mentagrophytes.

  Regarding the antibacterial activity of 2-alkylimidazole derivatives, 1-dodecyl-2-methylimidazole and 2-undecylimidazole were reported in Antibacterial and Fungus, Vol. 8, p. 371-375, 1984 (Non-patent Document 1). Are Gram-positive bacteria such as Staphylococcus aureus, Micrococcus luteus, Gram-negative bacteria such as Escherichia coli and Salmonella typhi, Candida albicans (Candida albicans) and other yeasts exhibit strong antibacterial activity.

These alkylimidazole compounds are stable in aqueous solvents. However, when the alkylimidazole compound is allowed to coexist with the isothiazolone-based compound in an aqueous solvent, the stability of the alkylimidazole compound is decreased even though the isothiazolone-based compound is stable. Produces. Therefore, the commercial value is lowered and the activity of the alkylimidazole compound cannot be maintained at a high level over a long period of time. Such a problem occurs not only in the case of isothiazolone compounds but also in the case of coexisting with other active ingredients.
JP-A-5-286815 (Claims, Examples) JP-A-9-263504 (Claims) JP-A-9-124625 (Claims) JP-A-51-54925 (Claims, page 3, upper right column, line 5 to page 7, lower left column) Antibacterial fungus, Vol. 8, p. 371-375, 1984

  Accordingly, an object of the present invention is to provide a fungicide composition in which an alkylimidazole compound is stabilized even when an active ingredient having antimicrobial activity is present, and a method for stabilizing an alkylimidazole compound.

  Another object of the present invention is to provide a bactericide composition in which an alkylimidazole compound is stabilized and a method for stabilizing an alkylimidazole compound even when the ratio between the alkylimidazole compound and other active ingredients is in a wide range. There is.

  Still another object of the present invention is to provide a method capable of stabilizing an alkylimidazole compound in a coexistence system with other active ingredients by a simple operation.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that when an alkylimidazole compound and another active ingredient (such as an isothiazolone compound) have high stability alone, when both are combined in an aqueous solvent, Other active ingredients (such as isothiazolone compounds) maintain stability, but the stability of the alkylimidazole compound is greatly reduced. In such coexistence systems, oxidizing agents (such as halogen acids such as bromic acid and iodic acid, or these It was found that the stability of the alkylimidazole compound was greatly improved by adding a salt or the like, and the present invention was completed.

That is, the fungicidal composition of the present invention contains an alkylimidazole compound, an active ingredient having antimicrobial activity, an oxidizing agent, and a solvent (such as an aqueous solvent such as water). The alkylimidazole compound may be 1-C _8-16 alkyl-2-C _1-4 alkylimidazole. The active ingredient having antimicrobial activity may be an isothiazoline compound, haloacetylene compound, benzimidazole compound, nitroalcohol compound, dithiol compound, thiophene compound, halocyanoacetamide compound, etc., alone or in combination of two or more. Can be used. The weight ratio between the alkylimidazole compound and the active ingredient having antimicrobial activity can be selected from the range of the former / the latter = 99/1 to 1/99 (for example, 90/10 to 10/90).

  The oxidizing agent may be various oxidizing agents such as halogen acids or salts thereof, permanganic acid or salts thereof, peroxides, peroxo acids or salts thereof, metal salts, metal halides, and the like. The oxidizing agent may be at least one selected from hypohalous acid, halogen acid and perhalogen acid, or a salt thereof (such as alkali metal or ammonium salt). An oxidizing agent can be used individually or in combination of 2 or more types. The ratio of the oxidizing agent may be about 0.1 to 75 parts by weight (for example, 1 to 50 parts by weight) based on 100 parts by weight of the total amount of the alkylimidazole compound and the active ingredient having antimicrobial activity.

More specifically, the disinfectant composition contains an organic or inorganic acid in an aqueous solvent, 1-C _8-16 alkyl-2-C _1-4 alkylimidazole, and 2-C _1-10 alkyl. A weight ratio of the former / the latter = 90/10 to 10/90 with the isothiazolone compound selected from -4-isothiazolin-3-one and 5-halo-2-C _1-10 alkyl-4-isothiazolin-3-one And the proportion of the halogen acid or alkali metal salt thereof is 1 to 30 parts by weight with respect to 100 parts by weight of the total amount of 1-C _8-16 alkyl-2-C _1-4 alkylimidazole and isothiazolone compound. Good.

  In the present invention, an oxidant is added to a coexisting system in which an alkylimidazole compound and an active ingredient having antimicrobial activity coexist in a solvent (such as an aqueous solvent such as water), thereby improving the stability of the alkylimidazole compound. The method of improving and the method of controlling or preventing microorganisms using the said bactericide composition are also included. In addition, this invention is useful for applying to the coexistence system whose said active ingredient is a component which reduces the stability of the said alkylimidazole compound.

  In the present specification, the term “antimicrobial” is used to mean killing microorganisms such as bacteria, molds, and algae, inhibiting the growth of microorganisms, or preventing the generation of microorganisms. Further, “control” means inhibiting the death of microorganisms or the generation or growth of microorganisms. In this specification, “antimicrobial agents” may be collectively referred to simply as “bactericides”.

  In the present invention, even when other active ingredients having antimicrobial activity (such as bactericidal activity) coexist, the alkylimidazole compound can be stabilized by the oxidizing agent without impairing the activity and stability of the active ingredient. In addition, the alkylimidazole compound can be stabilized even when the ratio of the alkylimidazole compound and other active ingredients is in a wide range. Therefore, the activity by a plurality of active ingredients can be effectively expressed over a long period of time. Furthermore, the coexistence system of the alkylimidazole compound and other active components can be stabilized by a simple operation of adding an oxidizing agent.

  The fungicide composition of the present invention contains an alkylimidazole compound, an active ingredient having antimicrobial activity (such as a fungicide), an oxidizing agent, and an aqueous solvent, and the alkylimidazole compound is stable in an aqueous medium. It has become.

[Alkylimidazole compound]
The alkylimidazole compound is not particularly limited as long as it has antimicrobial activity such as bactericidal, antifungal, and algal control. For example, the alkylimidazole compound has about 4 to 50 carbon atoms, preferably about 6 to 40 carbon atoms. And more preferably a compound having about 10 to 30 carbon atoms. Such an alkylimidazole compound may be, for example, a compound represented by the following formula (1).

(In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom or an alkyl group. However, R ¹ and R ² are not both hydrogen atoms.)

The alkyl group represented by R ¹ can be selected from, for example, a linear or branched C _1-20 alkyl group, and is usually a linear or branched C _6-18 alkyl group (for example, C _{8- 16} alkyl group), preferably a C _9-15 alkyl group, and often a C _10-14 alkyl group (especially a linear C _11-13 alkyl group).

The alkyl group represented by R ² can be selected, for example, from a linear or branched C _1-20 alkyl group, and is usually a linear or branched C _1-10 alkyl group, preferably C _{1- A 6} alkyl group, more preferably a C _1-4 alkyl group, and a C _1-3 alkyl group in many cases.

Specific examples of the alkyl group represented by R ¹ and R ² include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Isopentyl, neopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Nonadecyl group, icosyl group and the like are exemplified.

Examples of the alkyl imidazole compound include 1-C _1-20 alkyl imidazole, 2-C _1-20 alkyl imidazole, 1-C _1-20 alkyl-2-C _1-20 alkyl imidazole (for example, 1-C _{6- 18} alkyl-2-C _1-10 alkyl imidazole, preferably 1-C _8-16 alkyl-2-C _1-6 alkyl imidazole, more preferably 1-C _9-15 alkyl-2-C _1-4 alkyl imidazole Etc.) and is usually 1-C _8-16 alkyl-2-C _1-4 alkylimidazole, for example, 1-C _10-14 alkyl-2-C _1-3 alkylimidazole.

Specific examples of the alkylimidazole compound include, for example, 1-alkylimidazole (for example, 1-methylimidazole, 1-ethylimidazole, 1-butylimidazole, 1-pentylimidazole, 1-hexylimidazole, 1-heptylimidazole, 1- 1-C _1-20 alkyl imidazoles such as octyl imidazole, 1-nonyl imidazole, 1-decyl imidazole, 1-dodecyl imidazole, 1-tetradecyl imidazole, 1-heptadecyl imidazole);
2-alkylimidazole (for example, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole, 2-butylimidazole, 2-hexylimidazole, 2-octylimidazole, 2-decylimidazole, 2-un 2-C _1-20 alkylimidazoles such as decylimidazole, 2-dodecylimidazole, 2-tetradecylimidazole, 2-heptadecylimidazole);
1,2-dialkylimidazole (eg, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-butyl-2-methylimidazole, 1-pentyl-2-methylimidazole, 1-hexyl-2-methyl Imidazole, 1-heptyl-2-methylimidazole, 1-octyl-2-methylimidazole, 1-nonyl-2-methylimidazole, 1-decyl-2-methylimidazole, 1-dodecyl-2-methylimidazole, 1-tetradecyl 1-C _1-20 alkyl-2-methylimidazoles such as 2-methylimidazole and 1-heptadecyl-2-methylimidazole;
1-methyl-2-ethylimidazole, 1,2-diethylimidazole, 1-butyl-2-ethylimidazole, 1-pentyl-2-ethylimidazole, 1-hexyl-2-ethylimidazole, 1-heptyl-2-ethyl Imidazole, 1-octyl-2-ethylimidazole, 1-nonyl-2-ethylimidazole, 1-decyl-2-ethylimidazole, 1-dodecyl-2-ethylimidazole, 1-tetradecyl-2-ethylimidazole, 1-heptadecyl 1-C _1-20 alkyl-2-ethylimidazoles such as 2-ethylimidazole;
1-methyl-2-propylimidazole, 1-ethyl-2-propylimidazole, 1-butyl-2-propylimidazole, 1-pentyl-2-propylimidazole, 1-hexyl-2-propylimidazole, 1-heptyl-2 -Propylimidazole, 1-octyl-2-propylimidazole, 1-nonyl-2-propylimidazole, 1-decyl-2-propylimidazole, 1-dodecyl-2-propylimidazole, 1-tetradecyl-2-propylimidazole, 1 1-C _1-20 alkyl-2-propylimidazoles such as heptadecyl-2-propylimidazole;
1-methyl-2-isopropylimidazole, 1-ethyl-2-isopropylimidazole, 1-butyl-2-isopropylimidazole, 1-pentyl-2-isopropylimidazole, 1-hexyl-2-isopropylimidazole, 1-heptyl-2 -Isopropylimidazole, 1-octyl-2-isopropylimidazole, 1-nonyl-2-isopropylimidazole, 1-decyl-2-isopropylimidazole, 1-dodecyl-2-isopropylimidazole, 1-tetradecyl-2-isopropylimidazole, 1 1-C _1-20 alkyl-2-isopropylimidazoles such as heptadecyl-2-isopropylimidazole;
1-methyl-2-butylimidazole, 1-ethyl-2-butylimidazole, 1,2-dibutylimidazole, 1-pentyl-2-butylimidazole, 1-hexyl-2-butylimidazole, 1-heptyl-2-butyl Imidazole, 1-octyl-2-butylimidazole, 1-nonyl-2-butylimidazole, 1-decyl-2-butylimidazole, 1-dodecyl-2-butylimidazole, 1-tetradecyl-2-butylimidazole, 1-heptadecyl 1-C _1-20 alkyl-2-butylimidazoles such as 2-butylimidazole;
1-C _1-20 alkyl-2-hexylimidazoles corresponding to the 1-C _1-20 alkyl-2-butylimidazoles, 1-C _1-20 alkyl-2-octylimidazoles, 1-C _{1- 20-alkyl-2-decyl} imidazole, 1-C _1-20 alkyl-2-undecyl imidazole, 1-C _1-20 alkyl-2-dodecyl imidazole, 1-C _1-20 alkyl-2-tetradecyl Imidazoles, 1-C _1-20 alkyl-2-heptadecyl imidazoles, etc.).

  The alkylimidazole compound is a known compound and can be produced by a known method. For example, 1,2-dialkylimidazole can be produced by reacting 2-alkylimidazole with an alkyl halide at 120-180 ° C. in the presence of an alkali metal hydroxide.

The alkylimidazole compounds can be used alone or in combination of two or more. Of these alkyl imidazole compounds, 1-C _6-20 alkyl-2-C _1-3 alkyl-imidazoles (eg, 1-C _6-18 alkyl-2-C _1-2 alkyl imidazole, especially C _{8 -16} alkyl-2- _C1-2 alkylimidazole) is preferred.

  The alkylimidazole compound exhibits high antimicrobial activity. In particular, even at low concentrations, the antimicrobial spectrum (antibacterial spectrum) is wide, and it has extremely high inhibitory activity against a wide variety of microorganisms.

[Active ingredient having antimicrobial activity]
The active ingredient that can be used in combination with the alkylimidazole compound is a component having antimicrobial activity (antimicrobial agent), for example, a bactericide [ie, a bactericidal agent, a preservative or a fungicide (a bactericidal or fungicidal component) , Algaecide] and the like. Among these active ingredients, the present invention is useful for application to a combination with an active ingredient that reduces the stability or activity of the alkylimidazole compound by coexistence in a solvent (particularly an aqueous medium). Such an active component is often a compound containing a carbonyl group, a carbamoyl group, a carbon-carbon triple bond, a halogen atom, a nitrogen atom or a sulfur atom, or a compound containing a combination of these groups, bonds and atoms. .

  Examples of such active ingredients include isothiazoline compounds, haloacetylene compounds, benzimidazole compounds, nitroalcohol compounds, dithiol compounds, thiophene compounds, halocyanoacetamide compounds, and the like. In addition, as the antimicrobial agent, 2,2-dibromo-3-nitrilopropionamide, tetrachloroisophthalonitrile, methylenebisthiocyanate, and the like can be used. These active ingredients can also be used alone or in combination of two or more.

  The isothiazoline compound is represented by the following formula (2) and / or (3).

(In the formula, R ^3a represents a hydrocarbon group or a hydrogen atom which may have a substituent. R ⁴ and R ⁵ independently represent a hydrocarbon group which may have a substituent, A halogen atom or a hydrogen atom, and R ⁴ and R ⁵ may combine with each other to form a ring)

(In the formula, R ^3b represents a hydrocarbon group or a hydrogen atom which may have a substituent, and ring A represents a benzene ring which may have a substituent)

In the formula (2), examples of the hydrocarbon group represented by R ^3a include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include linear or branched C ₁ such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl and dodecyl groups. _{An -18} alkyl group can be exemplified. Preferred alkyl groups are C _1-4 alkyl groups (particularly C _1-3 alkyl groups such as a methyl group), C _6-12 alkyl groups (particularly linear or branched C ₆ such as an n-octyl group). _-10 alkyl group).

Examples of the alkenyl group include C _2-10 alkenyl groups such as vinyl group, propenyl group, isopropenyl, and butenyl group, and examples of alkynyl groups include C _2-10 alkynyl groups such as ethynyl group and propynyl group. Examples of the cycloalkyl group include C _3-10 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of the aryl group include C _6-10 aryl groups such as phenyl and naphthyl groups, and examples of the aralkyl group include C _6-10 aryl-C _1-4 alkyl groups such as benzyl and phenethyl groups.

In the formula (2), examples of the hydrocarbon group represented by R ⁴ and R ⁵ include the same alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, and aralkyl group as those described above. The carbon number of the hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 18 carbon atoms that may have a substituent, particularly a hydrocarbon group having 1 to 6 carbon atoms that has no substituent (for example, And a linear or branched C _1-6 alkyl group, in particular, a linear or branched C _1-3 alkyl group).

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. A preferred halogen atom is a chlorine atom.

Examples of the divalent hydrocarbon group for bonding R ⁴ and R ⁵ together to form a ring include C ₁ such as methylene, ethylene, trimethylene, propylene, tetramethylene, ethylmethylene, pentamethylene, hexamethylene and the like. _-6 alkylene group.

R ⁴ and R ⁵ are preferably a halogen atom or a hydrogen atom, particularly a hydrogen atom.

In the formula (3), the hydrocarbon group represented by R ^3b is the same hydrocarbon group as R ^3a (for example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, etc.). Can be mentioned. R ^3b is often a linear or branched C _1-18 alkyl group (eg, a C _1-10 alkyl group), and is usually a linear or branched C _1-6 alkyl group (eg, a C _1-6 alkyl group) , N-butyl group and the like.

Examples of the substituent of the hydrocarbon group or benzene ring include halogen atoms and alkyl groups (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, etc.). C _1-4 alkyl group), hydroxyl group, alkoxy group, carboxyl group, alkoxycarbonyl group, carbamoyl group, acyl group, amino group, N, N-dialkylamino group, acylamino group, nitro group and the like. The preferred substituent is often a halogen atom or an alkyl group. These substituents are the same or different and may be substituted by 1 to 4, preferably 1 or 2. In many cases, the benzene ring represented by ring A does not have a substituent.

In the compound represented by the formula (2), as a preferred embodiment of the substituent, for example, R ^3a is a C _1-4 alkyl group or a C _6-12 alkyl group, and R ⁴ and R ⁵ are a halogen atom or hydrogen. The aspect which is an atom is mentioned.

In the compound represented by formula (3), as a preferred embodiment of the substituent, for example, R ^3b is a C _1-6 alkyl group (such as n-butyl group) or a hydrogen atom, and ring A has a substituent. An embodiment in which the benzene ring is not used.

The isothiazoline compound may be hydrophobic or hydrophilic. Specific examples of the hydrophobic isothiazoline compounds represented by the formulas (2) and (3) include, for example, 2-C _6-12 alkyl-4-isothiazolin-3-one (2-n-octyl-4-isothiazoline- 3-one, etc.), halo (2-C _6-12 alkyl-4-isothiazolin-3-one) [5-chloro-2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-n -Octyl-4-isothiazolin-3-one, 4,5-dioctyl-2-n-octyl-4-isothiazolin-3-one, etc.], R ⁴ and / or R ⁵ is a halogen atom _5-10 cycloalkyl-4-isothiazolin-3-one (such as 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one), 1,2-benzisothiazolin-3-one, N—C _{1- 6-alkyl-1,2} (Such as N-n-butyl-1,2-benzisothiazolin-3-one) emission zone isothiazolin-3-one and the like. As the hydrophobic isothiazoline compound, 2-n-octyl-4-isothiazolin-3-one is often used. These isothiazoline compounds may be used alone or in combination of two or more.

Specific examples of the hydrophilic isothiazoline compound represented by the formula (2) include 2-C _1-4 alkyl-4-isothiazolin-3-one (2-methyl-4-isothiazolin-3-one, 2-ethyl). -4-isothiazolin-3-one), halo (2-C _1-4 alkyl-4-isothiazolin-3-one) [e.g., 5-chloro-2-methyl-4-isothiazolin-3-one, 5- Chloro-2-ethyl-4-isothiazolin-3-one etc.], 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one and the like. 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 compounds, 2-methyl-4-isothiazolin-3-one is often used as the hydrophilic compound. These inch azoline compounds may be used alone or in combination of two or more.

As the isothiazolone compound, a compound selected from 2-C _1-10 alkyl-4-isothiazolin-3-one and 5-halo-2-C _1-10 alkyl-4-isothiazolin-3-one is usually used. There are many.

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

(In the formula, R ⁶ and R ⁷ independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, X ¹ represents a halogen atom, and m represents an integer of 0 or 1. )

In the formula (4), examples of the hydrocarbon group represented by R ⁶ and R ⁷ include the same alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, and aralkyl group as those described above for R ^3a and R ^3b. Is mentioned. A preferred hydrocarbon group is a hydrocarbon group having about 1 to 18 carbon atoms, particularly an alkyl group (for example, a linear or branched C _1-18 alkyl group). Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, neopentyl, s-pentyl, t-pentyl, hexyl, heptyl, and n-octyl. , C _1-10 alkyl groups such as isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl and the like. A preferred alkyl group is a linear or branched C _1-6 alkyl group (such as an n-butyl group). Examples of the substituent of the hydrocarbon group include the substituents exemplified in the section of the compound represented by the formula (2) or (3).

In the formula (4), examples of the halogen atom represented by X ¹ include fluorine, chlorine, bromine and iodine atoms. In preferred compounds, the halogen atom is usually an iodine atom.

In the compound of formula (4), a preferred embodiment is, for example, that R ⁶ and R ⁷ are both hydrogen atoms, one of R ⁶ and R ⁷ is a hydrogen atom and the other is a C _1-10 alkyl group, or R ⁶ And R ⁷ is a C _1-10 alkyl group, X ¹ is an iodine atom, and m is 1. More preferably, one of R ⁶ and R ⁷ is a hydrogen atom, the other is a C _1-10 alkyl group, X ¹ is iodine, and m is 1. Particularly preferably, one of R ⁶ and R ⁷ is a hydrogen atom, the other is a C _1-6 alkyl group (such as an n-butyl group), X ¹ is an iodine atom, and m is 1. Is mentioned.

Among the compounds represented by formula (4), examples of the acid amide derivative that is a haloacetylene compound of m = 0 include, for example, 3-chloropropiolic acid amide, N—C _1-10 alkyl-3-chloropropiolic acid amide (For example, N-methyl-3-chloropropiolic acid amide, N-ethyl-3-chloropropiolic acid amide, N-propyl-3-methylpropiolic acid amide, N-butyl-3-chloropropiolic acid Amide, N-hexyl-3-chloropropiolic acid amide, N-octyl-3-chloropropiolic acid amide, etc.), N-cyclohexyl-3-chloropropiolic acid amide, etc. (N-substituted-) 3-chloro Propiolic acid amide; for example, 3-bromopropiolic acid amide, N—C _1-10 alkyl-3-bromopropiolic acid amide (eg, N— Methyl-3-bromopropiolic amide, N-ethyl-3-bromopropiolic amide, N-propyl-3-bromopropiolic amide, N-butyl-3-bromopropiolic amide, N-hexyl- (N-substituted-) 3-bromopropiolic amides such as 3-bromopropiolic amide, N-octyl-3-bromopropiolic amide, etc., N-cyclohexyl-3-bromopropiolic amide; 3-iodopropiolic amide, N—C _1-10 alkyl-3-iodopropiolic amide (eg, N-methyl-3-iodopropiolic amide, N-ethyl-3-iodopropiolic amide N-propyl-3-iodopropiolic acid amide, N-butyl-3-iodopropiolic acid amide, N-hexyl-3 And (N-substituted-) 3-iodopropiolic amides such as N-cyclohexyl-3-iodopropiolic amide, and the like. . Preferred compounds are (N-substituted-) 3-iodopropiolic amides, for example N—C _1-6 alkyl-3-iodopropiolic amides such as N-butyl-3-iodopropiolic amide. .

Examples of the carbamate derivative that is a haloacetylene compound of m = 1 include 3-iodo-2-propynylalkyl carbamate such as 3-iodo-2-propynylmethyl carbamate, 3-iodo-2-propynylethyl carbamate, 3- 3-iodo-2-propynyl C _1-10 such as iodo-2-propynylpropylcarbamate, 3-iodo-2-propynylbutylcarbamate, 3-iodo-2-propynylhexylcarbamate, 3-iodo-2-propynyloctylcarbamate And 3-iodo-2-propynyl C _3-10 cycloalkyl carbamate such as alkyl carbamate and 3-iodo-2-propynyl cyclohexyl carbamate. Among these compounds, 3-iodo-2-propynyl C _1-6 alkyl carbamates such as 3-iodo-2-propynyl butyl carbamate are exemplified. These haloacetylene compounds can be used alone or in combination of two or more.

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

(In the formula, R ⁸ represents a hydrocarbon group or a hydrogen atom which may have a substituent. R ⁹ represents —NHCOOR ¹⁰ (R ¹⁰ represents a hydrocarbon group which may have a substituent. A carbamate group or a thiazolyl group represented by

In the formula (5), examples of the hydrocarbon group represented by R ⁸ include the same alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, and aralkyl groups as those described above for R ^3a and R ^3b. . A preferred hydrocarbon group is a hydrocarbon group having about 1 to 18 carbon atoms, particularly an alkyl group (for example, a linear or branched C _1-18 alkyl group). The alkyl group, preferably methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, s- butyl, C _1-4 alkyl group such as t- butyl. In particular, a C _1-3 alkyl group (such as a methyl group) is preferable. Examples of the substituent of the hydrocarbon group include the substituents exemplified in the section of the compound represented by the formula (2) or (3).

When R ⁸ is a hydrocarbon group which may have a substituent, carbonization which may have a substituent at any of the 4-position, 5-position, 6-position and 7-position of the benzimidazole ring A hydrogen group may be substituted. In the case where R ⁸ is a hydrogen atom, a hydrocarbon group is not substituted on any of the 4-position, 5-position, 6-position and 7-position of the benzimidazole ring, that is, in the formula (5), R 8 ^An embodiment in which ⁸ is a hydrogen atom is exemplified. The most preferred embodiment of R ⁸ is a hydrogen atom.

In —NHCOOR ¹⁰ (carbamate group) represented by R ⁹ , the hydrocarbon group optionally having a substituent represented by R ¹⁰ is the same alkyl group, alkenyl group, alkynyl as R ^3a and R ^3b. Group, cycloalkyl group, aryl group, aralkyl group and the like. A preferred hydrocarbon group is a hydrocarbon group having about 1 to 18 carbon atoms, particularly an alkyl group (for example, a linear or branched C _1-18 alkyl group). Examples of the alkyl group include C _1-4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl, particularly C _1-3 alkyl groups (methyl, ethyl groups, etc. ) Is preferred.

Examples of the thiazolyl group represented by R ⁹ include 2-thiazolyl, 4-thiazolyl, 5-thiazolyl and the like. A preferred thiazolyl group is a 4-thiazolyl group.

Specific examples of the benzimidazole compound represented by the formula (5) include C _1-4 such as methyl 2-benzimidazole carbamate and ethyl 2-benzimidazole carbamate when R ⁹ is a carbamate group represented by —NHCOOR ^10. Examples include alkyl 2-benzimidazole carbamate. Moreover, when R < ⁹ > is a thiazolyl group, 2- (4-thiazolyl) benzimidazole etc. are mentioned, for example. Of these compounds, the preferred compound is methyl 2-benzimidazole carbamate. These benzimidazole compounds can be used alone or in combination of two or more.

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

(Wherein R ¹⁰ represents a hydrocarbon group or a hydrogen atom, R ¹¹ represents a hydrocarbon group having a hydroxyl group, a halogen atom or a hydrogen atom, and R ¹² represents a hydrocarbon group or a halogen atom having a hydroxyl group. .)

In the formula (6), examples of the hydrocarbon group represented by R ¹⁰ include the same alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, and aralkyl groups as those described above for R ^3a and R ^3b. . A preferred hydrocarbon group is a hydrocarbon group having about 1 to 18 carbon atoms, particularly an alkyl group (for example, a linear or branched C _1-18 alkyl group). The alkyl group, preferably methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, s- butyl, C _1-4 alkyl group such as t- butyl.

In the formula (6), examples of the hydrocarbon group represented by R ¹² and R ¹³ include the same hydrocarbon groups as those exemplified for R ¹⁰ above. A preferred hydrocarbon group is an alkyl group. Examples of the alkyl group include C _1-4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl. The hydroxyl group may be substituted at an appropriate position of the hydrocarbon. For example, the hydrocarbon group is often substituted with 1 to 3 hydroxyl groups, preferably one hydroxyl group.

Examples of the hydrocarbon group having a hydroxyl group include hydroxy C _1-4 alkyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl. A preferred hydroxyalkyl group is a hydroxy C _1-3 alkyl group (such as a hydroxymethyl group).

In the formula (6), examples of the halogen atom represented by R ¹¹ and R ¹² include fluorine, chlorine, bromine and iodine atoms. Preferred halogen atoms are a chlorine atom and a bromine atom.

In Formula (6), a preferred embodiment is, for example, that R ¹⁰ is a C _1-4 alkyl group (such as a methyl group) or a hydrogen atom, and R ¹¹ is a C _1-4 alkyl group having a hydroxyl group (hydroxymethyl). , Hydroxylethyl group, etc.), a halogen atom (bromine atom, chlorine atom, particularly bromine atom) or a hydrogen atom, and R ¹² is a C _1-4 alkyl group having a hydroxyl group (such as hydroxylmethyl group), a halogen atom ( Bromine atom or chlorine atom).

  Specific examples of the nitroalcohol compound represented by the formula (6) include 2-bromo-2-nitropropane-1,3-diol, 2-bromo-2-nitrobutane-1,3-diol, and 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- Examples include 3-nitro-2-propanol, 2-chloro-2-nitroethanol, 2-chloro-2-nitro-1,3-propanediol, and 3-chloro-3-nitro-2-propanol. Of these compounds, 2-bromo-2-nitropropane-1,3-diol and 2,2-dibromo-2-nitro-1-ethanol are often used. These nitroalcohol compounds can be used alone or in combination of two or more.

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

(Wherein X ² and X ³ independently represent a halogen atom or a hydrogen atom)

In formula (7), examples of the halogen atom represented by X ² and X ³ include fluorine, chlorine, bromine and iodine atoms. Preferred halogen atoms are a chlorine atom and a bromine atom.

In Formula (7), 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 chlorine. One of the atoms, X ² and X ³ is a bromine atom, 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.

  Specific examples of the dithiol compound represented by the following Take (7) 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 and the like can be mentioned. Of these compounds, 4,5-dibromo-1,2-dithiol-3-one is often used. These dithiol compounds can be used alone or in combination of two or more.

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

(In the formula, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ independently represent a hydrocarbon group, a halogen atom or a hydrogen atom which may have a substituent.)

In the formula (8), as the hydrocarbon group represented by R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ , the same alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group as those described above for R ^3a and R ^3b And an aralkyl group. A preferred hydrocarbon group is a hydrocarbon group having about 1 to 18 carbon atoms, particularly an alkyl group (for example, a linear or branched C _1-18 alkyl group). The alkyl group, preferably methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, s- butyl, C _1-4 alkyl group such as t- butyl. Examples of the substituent of the hydrocarbon group include the substituents exemplified in the section of the compound represented by the formula (2) or (3).

Examples of the halogen atom represented by R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ include fluorine, chlorine, bromine and iodine, preferably chlorine.

In the formula (8), a preferred embodiment is that R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are all halogen atoms, R ¹³ , R ¹⁴ and R ¹⁵ are halogen atoms, R ¹⁶ is a hydrogen atom, R ¹³ and R ^{16 14} is a halogen atom, and R ¹⁵ and R ¹⁶ are hydrogen atoms. Among such embodiments, preferred is an embodiment in which all of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are halogen atoms, and in particular, all of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are chlorine atoms.

  Specific examples of the thiophene compound represented by the formula (8) include, for example, 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1-dioxide, 3,3,4,4-tetrabromotetrahydrothiophene- 1,1-dioxide 3,4-dichlorotetrahydrothiophene-1,1-dioxide, 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide, 3,3,4-tribromotetrahydrothiophene-1,1- Examples include dioxide. Of these compounds, 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide are often used. These thiophene compounds can be used alone or in combination of two or more.

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

(In the formula, X ⁴ and X ⁵ independently represent a halogen atom or a hydrogen atom. R ¹⁷ represents a hydrocarbon group which may have a substituent.)

In the formula (9), examples of the halogen atom represented by X ⁴ and X ⁵ include fluorine, chlorine, bromine and iodine atoms. A preferred halogen atom is a bromine atom.

In the formula (9), examples of the hydrocarbon group represented by R ¹⁷ include the same alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, aralkyl group and the like as R ^3a and R ^3b . A preferred hydrocarbon group is a hydrocarbon group having about 1 to 18 carbon atoms, particularly an alkyl group (for example, a linear or branched C _1-18 alkyl group). The alkyl group, preferably methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, s- butyl, C _1-4 alkyl group such as t- butyl. Examples of the substituent of the hydrocarbon group include the substituents exemplified in the section of the compound represented by the formula (2) or (3).

  Specific examples of the halocyanoacetamide compound represented by the formula (9) include, for example, monochromocyananoacetamide, monobromocyanoacetamide, dichlorocyanoacetamide, dibromocyanoacetamide, monochloromonofluorobromoacetamide, N-methyldibromocyanoacetamide and the like. Is mentioned. Of these compounds, dibromocyanoacetamide is often used. These halocyanoacetamide compounds can be used alone or in combination of two or more.

  Each compound can be produced by a known method or a method analogous thereto. Each active compound may be used in a free form or as a salt (a salt with an acid or an alkali).

  The weight ratio between the alkylimidazole compound and the active ingredient having antimicrobial activity can be selected from a wide range that does not impair the antimicrobial activity. For example, the former / the latter = 99/1 to 1/99 (for example, 95/5 to 5). / 95), preferably 90/10 to 10/90, more preferably about 80/20 to 20/80 (for example, 30/70 to 70/30), and about 25/75 to 50/50. Also good.

[Oxidant]
As the oxidizing agent, various oxidizing agents such as halogen acid or its salt, permanganic acid or its salt, peroxide, peroxo acid or its salt, metal salt, metal halide and the like can be used. These oxidizing agents can be used alone or in combination of two or more.

  The halogen acid includes at least one selected from hypohalous acid, halogen acid and perhalogen acid. Examples of hypohalous acid include hypochlorous acid, hypobromous acid, and hypoiodous acid. Examples of halogen acid include chloric acid, bromic acid, and iodic acid. Examples of perhalogen acid include perchlorine. Examples thereof include acid and periodic acid. Halogen acids can be used in free form or in salt form. Examples of the halogen acid salt include alkali metal salts (lithium, potassium, sodium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), ammonium salts, and the like. Preferred salts are alkali metal salts or ammonium salts.

  Halogen acids or their salts can be used alone or in combination of two or more. A preferred halogen acid or a salt thereof is an alkali metal or ammonium salt of a halogen acid, and usually a halogen acid or an alkali metal salt thereof is often used.

  Specific examples of the halogen acid or a salt thereof include, for example, chloric acid or a salt thereof (sodium hypochlorite, potassium hypochlorite, sodium chlorate, potassium chlorate, ammonium chlorate, sodium perchlorate, perchlorine). Potassium etc.), bromic acid or salts thereof (sodium hypobromite, potassium hypobromite, sodium bromate, potassium bromate, ammonium bromate, etc.), iodic acid or salts thereof (sodium hypoiodite, next Examples thereof include potassium iodate, sodium iodate, potassium iodate, ammonium iodate, sodium periodate, and potassium periodate).

  Examples of permanganic acid or a salt thereof include sodium permanganate and potassium permanganate. Examples of the metal salt include copper sulfate, copper acetate, and bismuth acetate, and examples of the metal halide include iron trichloride and copper dichloride.

  Examples of peroxides include hydrogen peroxide, diacyl peroxide (eg, acetyl peroxide, benzoyl peroxide, lauroyl peroxide), dialkyl peroxide (eg, t-butyl peroxide, dicumyl peroxide), and alkyl hydroperoxide (t- Examples thereof include butyl peroxide and cumene hydroperoxide) and alkylidene peroxide (such as ethyl methyl ketone peroxide). Examples of peroxo acids or salts thereof include peracids (for example, perorganic carboxylic acids such as performic acid, peracetic acid, pertrifluoroacetic acid, perbenzoic acid), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.) And the like.

  The ratio of the oxidizing agent can be used in a wide range that can improve the stability of the alkylimidazole compound. For example, 0.1 to 75 weights with respect to 100 weight parts of the total amount of the alkylimidazole compound and the active ingredient having antimicrobial activity. Parts (for example, 1 to 50 parts by weight), preferably 1 to 30 parts by weight (for example, 2 to 30 parts by weight), more preferably about 3 to 20 parts by weight, and usually 2 to 10 parts by weight (for example, 3 to 10 parts by weight), particularly about 5 to 10 parts by weight. The ratio of the oxidizing agent to 100 parts by weight of the alkylimidazole compound may be, for example, 0.1 to 300 parts by weight (for example, 1 to 250 parts by weight), preferably about 5 to 250 parts by weight. It is about 5 to 50 parts by weight (5 to 40 parts by weight), particularly about 5 to 30 parts by weight (for example, 10 to 30 parts by weight).

[solvent]
The disinfectant composition of the present invention is often used as a liquid (for example, a wettable powder, an aqueous solvent, a suspension, a dispersant, an emulsion, an oil, a coating agent, a spray, an aerosol, etc.). The solvent of the liquid agent may be various solvents capable of dissolving or dispersing the active ingredient, that is, an aqueous solvent (or hydrophilic solvent) or an oily solvent (or hydrophobic solvent), and water and / or an organic solvent may be used. Can be used. The solvent may be water alone or in combination with an organic solvent. Organic solvents include alcohols, ethers, ketones, esters, carboxylic acids, nirolyls, halogenated hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, aprotic Various organic solvents such as a polar solvent are included. These organic solvents can be used alone or in combination of two or more. The organic solvent may be a water-soluble solvent (hydrophilic solvent), a water-miscible solvent, or a water-insoluble solvent (hydrophobic solvent).

Examples of the water-soluble solvent include alcohols [for example, C ₁ such as monohydric alcohol (eg, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol). _-4 alkanols, etc.), dihydric or polyhydric alcohols (C _1-4 alkane di to polyols such as glycerin, ethylene glycol, propylene glycol, etc.), etc .; ethers [eg, cyclic ethers (eg, C such as dioxane, tetrahydrofuran, etc.) _4-8 cyclic ethers), mono- or di-alkylene glycol monoalkyl ethers (e.g., ethylene glycol monomethyl ether, cellosolve such as ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, carbitols such as diethylene glycol monobutyl ether, etc.)]; ketones (eg, acetone); esters; carboxylic acids (formic acid, acetic acid, etc.); aprotic polar solvents (eg, nitriles such as acetonitrile) , N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, pyridine, etc.). These water-soluble solvents can be used alone or in combination.

  Examples of the water-insoluble solvent include alcohols (for example, monohydric alcohols such as hexanol, n-octanol, 2-butyloctanol, lauryl alcohol, cyclohexanol); ethers (for example, ethyl ether, propyl ether, isopropyl). Ethers, chain ethers such as dimethoxyethane); ketones (eg, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.); esters (eg, ethyl acetate, butyl acetate, etc.); halogenated hydrocarbons (eg, carbon tetrachloride) , Chloroform, dichloromethane, 1,2-dichloroethane, etc.), aliphatic hydrocarbons (eg, hexane, octane, etc.); alicyclic hydrocarbons (eg, cyclohexane, cycloheptane, etc.), aromatic hydrocarbons (eg, , Benzene, toluene, xylene, etc.); nitriles (e.g., benzonitrile) and the like. These water-insoluble solvents can be used alone or in combination.

Of these solvents, aqueous solvents (for example, water alone, mixed solvents of water and water-soluble solvents) are often used. Examples of water-soluble solvents include alcohols (for example, alcohols such as ethanol and isopropanol, ethylene glycol). C _1-3 alkane di to polyol such as propylene glycol) and ethers (for example, cellosolves and carbitols such as diethylene glycol monomethyl ether) are widely used.

  The ratio of water and organic solvent (particularly water-soluble solvent) is not particularly limited, and can be used in the range of water / organic solvent (weight ratio) = 100/0 to 0/100, for example, water / organic solvent (weight). Ratio) = 100/0 to 10/90, preferably about 100/0 to 20/80.

  A preferred solvent is an aqueous solvent, particularly water that does not contain a water-soluble organic solvent (including the alcohol, the water-soluble glycol solvent, etc.) in order to reduce the burden on the environment.

  Moreover, when using an active ingredient with low water solubility (for example, a water-insoluble or poorly water-soluble alkylimidazole compound), a salt with an alkali or an acid may be formed as necessary to improve water solubility. As the alkali, organic bases (such as amines such as trialkylamines and alkanolamines) and inorganic bases (such as alkali metal hydroxides such as ammonia, sodium hydroxide and potassium hydroxide, alkali metal carbonates) can be used.

  In the composition of the present invention containing an alkylimidazole compound, it is advantageous to combine an alkylimidazole compound and an acid to improve the water solubility of the alkali imidazole compound. In particular, when an aqueous solvent (for example, water alone, a mixed solvent of water and the water-soluble solvent; preferably water alone) is used, it is advantageous to use an acid in order to neutralize the alkylimidazole compound.

  The acid may be a water-soluble inorganic acid or a water-soluble organic acid (such as an organic carboxylic acid). Examples of the water-soluble inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like. The water-soluble organic acid may be a sulfonic acid (an alkane sulfonic acid such as methane sulfonic acid, an arene sulfonic acid such as toluene sulfonic acid or benzene sulfonic acid), but is often an organic carboxylic acid. The organic carboxylic acid may be, for example, an organic carboxylic acid having 1 to 6, preferably 1 to 5, more preferably 1 to 4, particularly 1 to 3 carbon atoms. Examples of the organic carboxylic acid include monovalent carboxylic acids such as formic acid, acetic acid and butyric acid, divalent carboxylic acids such as oxalic acid and succinic acid, and hydroxycarboxylic acids such as lactic acid. An acid can be used individually or in combination of 2 or more types.

  The amount of the acid used depends on the type of active ingredient (for example, alkylimidazole compound), its content, the type of solvent, and the like. It can be selected from a wide range of 2 equivalents, for example, 0.005 to 0.8 equivalents (for example, 0.01 to 0.5 equivalents), preferably 0.01 to 0.7 equivalents (for example, 0.02 to 0). .4 equivalents), more preferably 0.02 to 0.6 equivalents (for example, 0.03 to 0.3 equivalents), particularly about 0.05 to 0.2 equivalents. Even if the amount of acid used is small, the alkylimidazole compound can be solubilized in water.

  The pH of the fungicidal composition of the present invention due to the addition of acid is, for example, less than 8 (for example, 3 or more and less than 8), preferably 4 to 7.7, and more preferably about 5 to 7.5. May be. When the pH is 8 or more, the alkylimidazole compound is likely to precipitate.

  The disinfectant composition contains various additives, for example, surfactants; stabilizers such as antioxidants and UV absorbers; thickeners; flow aids; UV scattering agents; May be. Furthermore, the fungicide composition of the present invention may be used in combination with other fungicides, antiseptics, fungicides, algicides, herbicides, insecticides and the like.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. In addition, even if it does not contain surfactant, it can melt | dissolve or disperse | distribute stably in a solvent (especially aqueous solvent), without depositing a disinfectant composition. Therefore, the load on the environment can be further reduced.

Nonionic surfactants include polyoxyethylene alkyl ethers (for example, polyoxyethylene C _6-24 alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, and polyoxyethylene cetyl ether), polyoxyethylene Alkyl aryl ethers (for example, polyoxyethylene C _6-18 alkyl C _6-12 aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether), ethers such as polyoxyethylene-polyoxypropylene block copolymers Type nonionic surfactant: polyhydric alcohol [(poly) glycerin, trimethylolpropane, propylene glycol, pentaerythritol, sorbitan, sorbitol, glycerin, Polyhydric alcohol fatty acid esters and the like] and the fatty acid esters (e.g., glycerol C _8-24 fatty acid ester such as glycerin monostearate, sucrose C _8-24 fatty acid esters such as sucrose monostearate, sorbitan monooleate Ester-type nonionic surfactants such as sorbitan C _8-24 fatty acid esters such as acid esters; polyoxyethylene polyhydric alcohol fatty acid esters (for example, polyoxyethylene glyceryl stearate esters, polyoxyethylene glycerin oleate esters, etc. polyoxyethylene glycerin C _8-24 fatty acid esters, polyoxyethylene sorbitan C _8-24 fatty acid esters such as polyoxyethylene sorbitan stearic acid ester, and polyoxyethylene sucrose C _8-24 fatty acid esters) etc. d The ether ether type nonionic surfactant, etc. In addition, in the said nonionic surfactant, the average addition mole number of oxyethylene (or ethylene oxide) is 1-35 mol, Preferably it is 2-30 mol, More preferably Is about 5 to 20 moles.

Anionic surfactants include metal soaps, sulfate metal salts such as alkyl sodium sulfate, alkyl benzene sulfonic acid metal salts (eg, C _6-24 alkyl benzene sulfonate), alkyl naphthalene sulfonic acid metal salts (eg, Di-C _3-8 alkylnaphthalene sulfonate, etc.), dialkyl metal salts of sulfosuccinate (eg, di-C _6-24 alkyl sodium 2-sulfosuccinate), lignin sulfonate metal salts, polyoxyethylene distyrenated phenyl ether sulfate Ammonium salts, polycarboxylic acid type surfactants and the like are included.

  In the anionic surfactant, examples of the metal salt include salts with alkali metals (for example, sodium and potassium) and alkaline earth metals (for example, magnesium and calcium).

  Examples of the antioxidant include 4,4'-thiobis-6-t-butyl-3-methylphenol, butylated hydroxyanisole (2-t-butyl-4-methoxyphenol and 3-t-butyl-4- A mixture of methoxyphenol), p-octylphenol, mono (or di or tri)-(α-methylbenzyl) phenol, 2,6-di-t-butyl-p-cresol (BHT), pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] phenolic antioxidants such as propionate; amine antioxidants such as N, N'-di-2-naphthyl-p-phenylenediamine; Hydroquinoline-based antioxidants such as 1,5-di (t-amyl) hydroquinoline; Sulfur-based oxidation such as dilauryl thiodipropionate Inhibitors: Phosphorous antioxidants such as triphenylphosphite can be exemplified.

  Examples of the ultraviolet absorber include benzotriazole compounds such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole; Benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone; salicylic acid compounds such as phenyl salicylate and pt-butylphenyl salicylate; 2-ethylhexyl 2-cyano-3,3 -Diphenyl acrylate, 2-ethoxy-2'-ethyl oxalic acid bisanilide, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, etc. It is done.

  Examples of the thickener include polyvinyl alcohol, polyacrylic acid and its salt. Examples of the flow aid include PAP aid (for example, isopropyl phosphate), polyethylene, fatty acid metal salt, organic lubricant such as wax, paraffin and silicone oil, and inorganic lubricant such as talc. Examples of the ultraviolet scattering agent include titanium dioxide. Examples of the colorant include organic or inorganic pigments and dyes.

  The usage-amount of an additive can be suitably selected according to the dosage form of a disinfectant composition, and the kind of additive. For example, the amount of the surfactant used is, for example, 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight with respect to 100 parts by weight of the alkylimidazole compound in the case of a liquid. .

  In the fungicide composition of the present invention, the content of the whole active ingredient (alkyl imidazole compound and other active ingredients) can be selected from the range of about 0.01 to 50% by weight, and 0.05 to 40% by weight (for example, 1 to 40% by weight), preferably 0.1 to 30% by weight (eg 3 to 30% by weight), more preferably about 5 to 25% by weight (eg 5 to 20% by weight). . In the case of an aerosol agent, the concentration of the active ingredient in the filling filled in the container is, for example, 0.01 to 30% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight. % May be sufficient.

  The bactericidal composition of the present invention is a combination of an alkylimidazole compound and other active ingredients, and even at low concentrations, it has a wide antimicrobial spectrum and can exhibit high microbicidal activity (such as bactericidal activity). . In particular, since the stability is high, high microbicidal activity can be expressed over a long period of time. Moreover, since the disinfectant composition of the present invention does not require a surfactant and an organic solvent, the burden on the environment can be reduced in all processes such as the production process, storage process, use and disposal.

  The fungicidal composition of the present invention comprises an alkyl imidazole compound, another active ingredient (for example, an active ingredient having antimicrobial activity and reducing the stability of the alkyl imidazole compound), an oxidizing agent, a solvent, Can be prepared by mixing. In particular, the stability of the alkylimidazole compound can be improved by adding an oxidizing agent. Therefore, the present invention provides an oxidant in a coexisting system in which an alkylimidazole compound and an active ingredient having antimicrobial activity and lowering the stability of the alkylimidazole compound coexist in a solvent (particularly an aqueous solvent). A method for improving the stability of the alkylimidazole compound is also provided.

  Furthermore, when an aqueous solvent (especially water) is used as the solvent, the water solubility of the alkylimidazole compound can be increased by adding the acid (especially a small amount of acid), and an aqueous composition can be obtained. In particular, a solubilized and stable aqueous composition can be obtained without substantially using an organic solvent (water-soluble organic solvent) or a surfactant. Therefore, the load on the environment can be greatly reduced.

  In the method of the present invention, the plurality of components may be simply mixed, or at least a part of components (alkyl imidazole compound and the like) may be previously solubilized in a solvent (for example, an aqueous solvent), and the components may be mixed. Good. For example, the liquid preparation can be prepared by mixing and diluting the alkylimidazole compound, the active ingredient, and the oxidizing agent together with a surfactant and other additives, if necessary, with an appropriate liquid diluent or carrier. In the case of a wettable powder, a solid carrier or a solid diluent may be further used. In the case of aerosol agents, propellants such as liquefied gases (fluorinated hydrocarbons, hydrocarbons, liquefied petroleum gas, dimethyl ether, etc.), compressed gases (inert gases such as nitrogen gas, carbon dioxide, etc.) are appropriately used. Can be used.

[Sterilization method]
The bactericidal composition of the present invention exhibits a broad antimicrobial spectrum (or bactericidal spectrum), can be effectively used as an antibacterial agent, fungicide, preservative, and the like, and is useful for controlling or preventing microorganisms. Therefore, even if it is a to-be-processed body (or to-be-processed area) in which a wide variety of harmful microorganisms exist, one kind of bactericidal composition is applied (added, applied, etc.) to the to-be-processed body (or to-be-processed area). Therefore, microorganisms can be controlled efficiently. Furthermore, generation | occurrence | production and growth of the microorganisms in a to-be-processed body (or to-be-processed area) can be prevented beforehand (or prevented).

  The disinfectant composition can be used at an appropriate temperature (for example, about −20 ° C. to 50 ° C.) and is usually used at room temperature (for example, about 10 to 35 ° C.). Examples of the object to be treated include various industrial water (water used in a paper pulp factory, cooling water used in a cooling water circulation process, etc.), metal processing oil (cutting oil, etc.), aqueous or hydrophilic materials ( Casein, starch paste, glue, synthetic rubber latex, synthetic resin emulsion, etc.), coating material (paper coating liquid, surface sizing agent, water-based paint, emulsion paint, water-based or hydrophilic coating materials such as water-based printing ink; Organic solvent-type coating materials such as organic solvent-type paints for indoor or outdoor use), adhesives (water-based or hydrophilic adhesives, oil-based adhesives, etc.), film materials (coated paper, polyvinyl alcohol film, polyvinyl chloride film, etc.) , Plastic products (housings such as housings and casings), cement admixtures, building materials (eg gypsum board, plaster) Ceiling materials, fiber wall, various joints, sealants, such as wallpaper), and the like. In addition, when used as an algae-proofing agent, the treated area is not limited to, for example, various water areas (for example, sea, rivers, lake water, etc.), but various above-ground areas where algae occur [for example, paddy fields, river beds, turf land (Especially, green of a golf course) and the like, and the surface or wall surface of various buildings (various buildings such as factories, houses, warehouses; various transport bodies such as vehicles, ships, and aircraft).

  The application amount (addition amount, application amount, etc.) of the disinfectant composition can be selected according to the object to be treated, and is usually converted into an active ingredient (or disinfectant) with respect to 100 parts by weight of the object to be treated, For example, it may be about 0.001 to 1 part by weight, preferably about 0.001 to 0.5 part by weight, and more preferably about 0.01 to 0.5 part by weight. For example, when the object to be treated is industrial water or the like, the application amount is, for example, 0.1 to 30,000 ppm, preferably 0.5 to 10,000 ppm in the object to be treated, in terms of active ingredient. Preferably, it may be about 1 to 5,000 ppm.

Furthermore, when applying a disinfectant composition to a treatment area having a two-dimensional extension, the amount of the disinfectant composition applied is, for example, in terms of active ingredient, per area of the treatment area, for example, 0.01 to 15 g / m ^2, preferably 0.05 to 10 g / m ^2, more preferably about 0.1-5 g / m ^2.

  INDUSTRIAL APPLICABILITY The present invention is useful for controlling or preventing microorganisms such as bacteria, fungi (fungi), yeast, and algae, and can be effectively used as an antibacterial agent, fungicide, preservative, algae and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
1 g of 1-dodecyl-2-methylimidazole (DMI), 2 g of 2-methyl-4-isothiazolin-3-one (MIT), 0.4 g of acetic acid, 0.2 g of sodium periodate (NaIO ₄ ), and water 96. 4 g was mixed to prepare a bactericidal composition. In addition, 1-dodecyl-2-methylimidazole (DMI) was dissolved, and a uniform fungicide composition (uniform solution) was obtained.

Examples 2-6
1-dodecyl-2-methylimidazole (DMI), 2-methyl-4-isothiazolin-3-one (MIT), acetic acid, sodium periodate (NaIO ₄ ) or sodium bromate (NaBrO ₃ ), and water 1 was mixed to prepare a bactericide composition. In Examples 2 to 6 and Comparative Examples 1 and 2, 1-dodecyl-2-methylimidazole (DMI) was dissolved, and a uniform fungicide composition (uniform solution) was obtained.

  And after enclosing the obtained bactericidal composition in a transparent container and storing at 60 ° C. for 1 week, the appearance was observed, the remaining amount of the active ingredient was measured by high performance liquid chromatography, and the remaining rate was calculated. . The results are shown in Table 1.

Examples 7-18
1-dodecyl-2-methylimidazole (DMI), 2-methyl-4-isothiazolin-3-one (MIT), acetic acid, potassium bromate (KBrO ₃ ), and water were mixed in the proportions shown in Table 2 and Table 3. Then, a bactericide composition was prepared. In these examples, 1-dodecyl-2-methylimidazole (DMI) was dissolved, and a uniform fungicide composition (uniform solution) was obtained.

  And when the stability of the obtained disinfectant composition was examined in the same manner as in the above Examples, the results shown in Table 2 and Table 3 were obtained.

Comparative Examples 1-12
Without using an oxidizing agent, 1-dodecyl-2-methylimidazole (DMI), 2-methyl-4-isothiazolin-3-one (MIT), acetic acid, and water were mixed in the proportions shown in Tables 4 and 5. A bactericidal composition was prepared.

  And when the stability of the obtained disinfectant composition was examined in the same manner as in the above Examples, the results shown in Table 4 and Table 5 were obtained.

  As is clear from the comparison between Tables 1 to 3 and Table 4, the fungicide compositions of the examples not only have less discoloration than the compositions of the comparative examples, but also have a high residual rate and high stability. Further, as is clear from Table 4, the stability of 1-dodecyl-2-methylimidazole (DMI) is lower than that of 2-methyl-4-isothiazolin-3-one (MIT).

  As is clear from the comparison between Tables 1 to 3 and Table 5, 1-dodecyl-2-methylimidazole (DMI) or 2-methyl-4-isothiazolin-3-one (MIT) alone is relatively stable. In a system in which both are present, the stability of 1-dodecyl-2-methylimidazole (DMI) decreases.

Claims (7)

A bactericide composition comprising an alkylimidazole compound, an isothiazoline compound having antimicrobial activity, a halogen acid or a salt thereof, and an aqueous solvent. Alkyl imidazole _{compound, 1-C 8-16} alkyl _{-2-C 1-4} alkyl imidazole according to claim 1 disinfectant composition. The fungicidal composition according to claim 1, wherein the weight ratio of the alkylimidazole compound and the isothiazoline compound having antimicrobial activity is the former / the latter = 99/1 to 1/99. The fungicidal composition according to claim 1, wherein the proportion of the halogen acid or a salt thereof is 0.1 to 75 parts by weight based on 100 parts by weight of the total amount of the alkylimidazole compound and the isothiazoline compound having antimicrobial activity. In an aqueous solvent, containing an organic or inorganic acid, 1-C _8-16 alkyl-2-C _1-4 alkylimidazole, 2-C _1-10 alkyl-4-isothiazolin-3-one and 5-halo- An isothiazolone compound selected from 2-C _1-10 alkyl-4-isothiazolin-3-one at a weight ratio of the former / the latter = 90/10 to 10/90, and the ratio of the halogen acid or its alkali metal salt is The fungicidal composition according to claim 1, wherein the amount is 1 to 30 parts by weight based on 100 parts by weight of the total amount of 1-C _8-16 alkyl-2-C _1-4 alkylimidazole and isothiazolone compound. A method of improving the stability of the alkylimidazole compound by adding a halogen acid or a salt thereof to a coexisting system in which a alkylimidazole compound and an isothiazoline compound having antimicrobial activity coexist in a solvent.   A method for controlling or preventing microorganisms using the bactericidal composition according to claim 1.