JP2003055116A - Industrial microbicident composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly safe industrial microbicident composition having a wide antimicrobial spectrum and high antimicrobial potency and thus having excellent antimicrobial effect with small amounts in use. SOLUTION: This industrial microbicide composition comprises as the active ingredients benzisothiazoline-based compound(s) and benzimidazole-based compound(s).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an industrial bactericidal composition, and more particularly to an industrial bactericidal composition suitable for use as a control agent for bacteria, fungi, yeasts, algae and the like.

[0002]

2. Description of the Related Art Conventionally, various industrial waters such as paper pulp mills and cooling water circulation processes, metal working oils such as cutting oils, casein, starch paste, glue, coated paper, paper coating liquid, surface In various industrial products such as sizing agents, paints, adhesives, synthetic rubber latex, printing inks, polyvinyl alcohol films, vinyl chloride films, plastic products, cement admixtures, harmful microorganisms easily propagate,
It is a cause of deterioration of productivity and quality, and generation of bad odor. Therefore, bactericides that exert a bactericidal effect are widely used to control the growth of such microorganisms. Many of such bactericides for industrial use are highly toxic, have a harmful effect on the human body, and have environmental pollution. Therefore, they cannot be used at a very high concentration. In addition, the antibacterial spectra of compounds are usually biased, and few show the same effectiveness against all microorganisms. There is also a problem that resistant bacteria appear when a single bactericide is used for a long period of time. Therefore, when these bactericides were used alone, in order to obtain a certain bactericidal effect against both filamentous fungi and bacteria, it was necessary to use a solution with a considerably high concentration in each case. Various compounds such as isothiazoline compounds, nitroalcohol compounds, dithiol compounds, thiophene compounds, and halocyanoacetamide compounds are known as such industrial germicides. However, even if the above-mentioned various compounds are used alone, their bactericidal effect is often insufficient, and in particular, resistant bacteria to these industrial bactericides also appear, and a sufficient bactericidal effect can be expressed. Development of new industrial fungicides is desired.

[0003]

The object of the present invention is to have a broad antibacterial spectrum and to show a significantly higher antibacterial activity against harmful microorganisms as compared with the case where each active ingredient is used alone. It is highly safe and provides excellent antibacterial and antifungal properties even when used in a small amount.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that
By containing a benzisothiazoline compound and a benzimidazole compound, and by further containing an isothiazoline compound in these,
It was found that these synergistic effects exert an antibacterial effect in an amount far smaller than the amount of the drug used alone, and further research based on this was completed, resulting in completion of the present invention.

That is, the present invention provides (1) an industrial bactericidal composition containing a benzisothiazoline compound and a benzimidazole compound, (2)
Further, an isothiazoline-based compound is contained as a bactericidal efficacy enhancer, wherein the industrial sterilization composition according to (1) above, and (3) a benzisothiazoline-based compound,
General formula (1);

[Chemical 4] (In the formula, Y ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and the A ₁ ring represents an optionally substituted benzene ring.) (1) or () 2) The industrial sterilizing composition described in (4) the general formula (1)
In the formula, Y ₁ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the benzene ring represented by the A ₁ ring is an unsubstituted benzene ring.
(5) The benzisothiazoline compounds are 1,2-benzisothiazolin-3-one and Nn-butyl-
The industrial bactericidal composition according to any one of the above (1) to (4), which is at least one of benzisothiazolin-3-one, (6) a benzimidazole-based compound represented by the general formula (2);

[Chemical 5] (Wherein, A ₂ ring represents a benzene ring which may be substituted, Z is -NHCOOR (wherein, R is a group represented by a hydrogen atom or an alkyl group.) Or may be substituted A compound represented by 5 or 6-membered nitrogen-containing heterocyclic group) or a salt thereof, wherein the industrial sterilizing composition according to any one of (1) to (5) above, (7) In formula (2), A ₂ ring is an unsubstituted benzene ring or a benzene ring substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R is a C _1-8 alkyl group. Or a Z is a thiazolyl group, the industrial bactericidal composition according to (6) above, (8) the benzimidazole compound is methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate and 2- (4- Chi (Azolyl) benzimidazole, which is at least one selected from the group consisting of the group consisting of (1) to (7), the industrial bactericidal composition according to any one of (1) to (9), wherein the isothiazoline-based compound has the general formula (3);

[Chemical 6] (Wherein R ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and R ₂ and R ₃ are the same or different and represent a hydrogen atom or a halogen atom). (1) R ₁ is a C _1-18 alkyl group, and R ₂ and R ₃ are the same or different and each is a hydrogen atom or a halogen atom. The industrial bactericidal composition according to the above (9), (11) an isothiazoline compound is 2-n-
Octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one, 4-chloro-2- n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one
On and 4,5-dichloro-2-n-octyl-4-
The industrial sterilizing composition according to any one of the above (1) to (10), which is at least one selected from the group consisting of isothiazolin-3-ones, (12) further containing water or / and a glycol solvent. (13) The industrial sterilizing composition according to any one of (1) to (11) above, which is used under conditions of pH value 7 to 11 (1) to (14) The industrial bactericidal composition according to any one of (12), (14) 1 to 400 parts by weight of a benzimidazole compound based on 100 parts by weight of a benzisothiazoline compound, (1), ( 3) to (8) and (12) to (13), the industrial sterilizing composition according to any one of (15) 100 parts by weight of a benzisothiazoline compound, and 1 to 400 parts by weight of a benzimidazole compound. Industrial fungicidal composition according to any one of the parts and isothiazoline compounds 1 to 200 parts by weight of above, wherein the blending (2) to (13), related.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the benzisothiazoline compound used in the present invention include compounds represented by the general formula (1).

[Chemical 7] (In the formula, Y ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and the A ₁ ring represents an optionally substituted benzene ring.) In the above formula (1), the substitution represented by Y ₁ The hydrocarbon group in the hydrocarbon group which may be formed has 1 to 2 carbon atoms.
A hydrocarbon group of 0, preferably 1 to 14 is preferable, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group and an aryl group. An alkyl group and a cycloalkyl group are preferred, and an alkyl group is more preferred.

Examples of the above alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, sec-octyl, tert-octyl, nonyl. , Carbon number such as decyl
There may be mentioned 10 alkyl groups. Preferably methyl,
1 to 1 carbon atoms such as ethyl, propyl, butyl and octyl
8 alkyl groups can be mentioned. More preferably, for example, methyl, n-butyl, n-octyl can be mentioned.

The above alkenyl group has, for example, 2 carbon atoms such as vinyl, allyl, isopropenyl, 1-propenyl, 2-propenyl and 2-methyl-1-propenyl.
~ 4 alkenyl groups. Preferably vinyl,
Examples include alkenyl groups having 2 to 3 carbon atoms such as allyl.

Examples of the alkynyl group include alkynyl groups having 2 to 5 carbon atoms such as ethynyl, 1-propynyl, 2-propynyl, butynyl and pentynyl. Preferably, it has 2 carbon atoms such as ethynyl and propynyl.
~ 3 alkynyl groups.

Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Preferably, it has 5 to 5 carbon atoms such as cyclopentyl and cyclohexyl.
And 6 cycloalkyl groups.

Examples of the above aryl group include aryl groups having 6 to 14 carbon atoms such as phenyl, naphthyl, anthryl and phenanthryl. Preferred is an aryl group having 6 carbon atoms such as phenyl.

Examples of the substituent of the optionally substituted hydrocarbon group represented by Y ₁ include a hydroxyl group, a halogen atom (eg chlorine, fluorine, bromine and iodine), a cyano group, an amino group, a carboxyl group. , An alkoxy group (for example, a C1-4 alkoxy group such as methoxy, ethoxy, propoxy, butoxy, etc.), an aryloxy group (for example, a C6-20 aryloxy group such as a phenoxy group), an alkylthio group (for example, , Methylthio, ethylthio, propylthio, butylthio and other C1-4 alkylthio groups) and C6
To 20 arylthio groups (eg, phenylthio groups, etc.)
And so on. Preferred are a halogen atom and an alkoxy group. These substituents may be the same or different and may be substituted by 1 to 5, preferably 1 to 3.

Of the above-mentioned optionally substituted hydrocarbon groups represented by Y ₁ , unsubstituted hydrocarbon groups are preferred, among which alkyl groups, especially methyl, ethyl, propyl, n-butyl are preferred. , N-octyl, and other alkyl groups having 1 to 8 carbon atoms are preferable, and methyl, n-butyl, and n-octyl are more preferable. Therefore, preferable examples of Y ₁ include a hydrogen atom, methyl, n-butyl and n-octyl.

In the benzisothiazoline compound represented by the above formula (1), the substituent of the benzene ring represented by A ₁ ring is a substituent of the optionally substituted hydrocarbon group represented by Y _1. Examples thereof include the same ones as described above, preferably a halogen atom and an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl). These substituents may be the same or different and may be substituted by 1 to 4, preferably 1 or 2.

Specific examples of the benzisothiazoline type compound represented by the above formula (1) include, for example, 1,2-benzisothiazolin-3-one (hereinafter abbreviated as BIT),
Nn-butyl-benzisothiazolin-3-one and the like can be mentioned.

The benzisothiazoline compounds used in the present invention are salts thereof, for example, alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, ammonia, ethylenediamine, 1,6.
It may be used in the form of a salt with an aliphatic amine such as hexamethylenediamine, an aromatic amine such as aniline, a heterocyclic amine such as pyridine, pyrrolidine, morpholine and methylpyridine. Of these salts, preferably, alkali metals such as sodium and potassium, ammonia,
Examples thereof include aromatic amines such as ethylenediamine and heterocyclic amines such as pyridine.

The benzisothiazoline compound used in the present invention can be produced by a known technique, but a commercially available product may be used. Examples of commercially available products include Proxel Press Paste P6 (trade name) (1,2-benzisothiazolin-3-one 80% by weight, manufactured by Avicia), Bankish 100 (trade name) (Nn-butyl-2-). Benzisothiazolin-3-one (95% by weight,
Manufactured by Abyssia) and the like.

The benzimidazole compound used in the present invention includes compounds represented by the general formula (2).

[Chemical 8] (In the formula, the A ₂ ring is an optionally substituted benzene ring,
Z represents a group represented by -NHCOOR (in the formula, R represents a hydrogen atom or an alkyl group) or an optionally substituted 5- or 6-membered nitrogen-containing heterocyclic group. ) In the benzimidazole compound represented by the above formula (2), the A ₂ ring represents an optionally substituted benzene ring.
Examples of the substituent of the benzene ring represented by A ₂ ring include a hydroxyl group and a halogen atom (for example, chlorine, fluorine,
Bromine and iodine), alkyl groups, alkenyl groups,
Examples thereof include an alkynyl group, a cycloalkyl group and an aryl group, and these substituents may be the same or different and may be substituted by 1 to 4, preferably 1 or 2.

Examples of the alkyl group as a substituent of the benzene ring represented by A ₂ ring include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl,
Examples thereof include alkyl groups having 1 to 10 carbon atoms such as octyl, isooctyl, sec-octyl, tert-octyl, nonyl and decyl. Preferably, methyl, ethyl, propyl, alkyl group having 1 to 4 carbon atoms such as butyl, particularly preferably methyl, ethyl, and a C _1-3 alkyl groups such as propyl.

Examples of the alkenyl group as the substituent of the benzene ring represented by A ₂ ring include vinyl, allyl,
Isopropenyl, 1-propenyl, 2-propenyl, 2
Examples thereof include alkenyl groups having 2 to 4 carbon atoms such as -methyl-1-propenyl. Preferred are alkenyl groups having 2 to 3 carbon atoms such as vinyl and allyl.

Examples of the alkynyl group as a substituent of the benzene ring represented by A ₂ ring include alkynyl groups having 2 to 5 carbon atoms such as ethynyl, 1-propynyl, 2-propynyl, butynyl and pentynyl. Preferred are alkynyl groups having 2 to 3 carbon atoms such as ethynyl and propynyl.

Examples of the cycloalkyl group as the substituent of the benzene ring represented by A ₂ ring include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
Examples thereof include cycloalkyl groups having 3 to 8 carbon atoms such as cycloheptyl and cyclooctyl. Preferred are cycloalkyl groups having 5 to 6 carbon atoms such as cyclopentyl and cyclohexyl.

The aryl group as the substituent of the benzene ring represented by A ₂ ring is, for example, phenyl, naphthyl, anthryl, phenanthryl and the like having 6 to 14 carbon atoms.
The aryl group of is mentioned. Preferred is an aryl group having 6 carbon atoms such as phenyl.

In the benzimidazole type compound represented by the above formula (2), Z is a group represented by --NHCOOR (R represents a hydrogen atom or an alkyl group) or an optionally substituted 5- or 6-membered group. Represents a nitrogen-containing heterocyclic group of. Examples of the alkyl group represented by R include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl. And a C _1-8 alkyl group such as C _{1-8 and} the like, and preferred examples include C such as methyl, ethyl, and n-propyl.
_1-3 alkyl groups can be mentioned.

Further, the nitrogen-containing heterocyclic group in the optionally substituted 5- or 6-membered nitrogen-containing heterocyclic group represented by Z in the benzimidazole compound represented by the above formula (2) is, for example, 5- or 6-membered containing 1 to 4 nitrogen atoms as ring-constituting atoms, or 1 to 2 nitrogen atoms plus 1 heteroatom selected from oxygen and sulfur as ring-constituting atoms Examples thereof include a monocyclic heterocyclic group having a ring and a condensed heterocyclic group in which a benzene ring or a 5-membered ring is condensed with the 5- or 6-membered nitrogen-containing heterocyclic ring. Specific examples of the 5- or 6-membered nitrogen-containing monocyclic heterocyclic group include, for example, pyridyl group (eg, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, etc.), thiazolyl group (eg, 2
-Thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, etc.), isothiazolyl group (for example, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, etc.), imidazolyl group (for example, 1-imidazolyl group,
2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, etc.), pyrrolyl group (2-pyrrolyl group, 3-pyrrolyl group, etc.), pyrrolinyl group (2-pyrrolinyl group, 3
-Pyrrolinyl group, etc.), flazanyl group (4-nitro-furan-3-yl, 4-methoxy-furan-3-yl, carboxymethyl-furan-3-yl etc.), pyrrolidinyl group (1-pyrrolidinyl group, 2- Pyrrolidinyl group, 3-pyrrolidinyl group, etc., imidazolidinyl group (2-imidazolidinyl group, 4-imidazolidinyl group,
5-imidazolidinyl group etc.), pyrazolidinyl group (eg 1-pyrazolidinyl group etc.), pyrazolyl group (eg 5-pyrazolyl group etc.), oxazolyl group (eg 2
-Oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, etc.), isoxazolyl group (3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, etc.), tetrazolyl group (e.g., 1H-tetrazolyl group, 2H-tetrazolyl group, etc.) ), Pyrimidyl group (for example, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, etc.), pyridazinyl group (for example, 3-pyridanidyl group, 4-pyridanidyl group, etc.), pyrazinyl group (2-
A pyrazinyl group, a 3-pyrazinyl group, a 5-pyrazinyl group,
6-pyrazinyl group), thiazinyl group (2-thiazinyl group, 3-thiazinyl group, 5-thiazinyl group, 6-thiazinyl group, etc.), piperazinyl group (2-piperazinyl group, 3-piperazinyl group, 5-piperazinyl group, 6-piperazinyl group), thiadiazinyl group (2-thiadiazinyl group, 3-thiadiazinyl group, 5-thiadiazinyl group, 6-thiadiazinyl group, etc.), oxadiazolyl group (for example, 1,3,4-oxadiazolyl group, 3- or 5-). (1,2,4-oxadiazolyl group etc.), thiadiazolyl group (eg 4- or 5- (1,2,3-thiadiazolyl group etc.), triazolyl group (eg 1,2,2,3)
3-triazolyl group, 1,2,4-triazolyl group, etc.), thiomorpholinyl group (2-thiomorpholinyl group,
3-thiomorpholinyl group, 5-thiomorpholinyl group, 6
-Thiomorpholinyl group, etc.), morpholinyl group (2-morpholinyl group, 3-morpholinyl group, 5-morpholinyl group, 6-morpholinyl group, etc.), oxoimidazolinyl group (2-oxoimidazolinyl group, etc.), di Oxotriazinyl group (1,2,4-dioxotriazinyl-3,5-
Dione-1-yl group, 1,2,4-dioxotriazinyl-3,5-dione-2-yl group, 1,2,4-dioxotriazinyl-3,5-dione-4- Group), piperidinyl group (2-piperidinyl group, 3-piperidinyl group, 4-piperidinyl group, 5-piperidinyl group, 6-piperidinyl group, etc.), 1,4-oxazinyl group (1,4
-Oxazinyl-2-yl, 1,4-oxazinyl-3
-Yl, etc.), piperazinyl group (2-piperazinyl group,
3-piperazinyl group, 4-piperazinyl group, 5-piperazinyl group and the like). Specific examples of the condensed heterocyclic group include, for example, quinolyl group (for example, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, etc.), isoquinolyl group (3-isoquinolyl group, 4-isoquinolyl group, etc.), indolyl group. Group (2-indolyl group, 3-indolyl group, etc.), isoindolyl group (1H-isoindol-3-yl group, etc.), quinolidinyl group (8-quinolidinyl group, etc.), purinyl group (1H-purin-6-yl, Three
H--purin-6-yl group), cinnolinyl group (3
-Cinnolinyl group, 5-cinnolinyl group and the like), indazolyl group (3-indazolyl group and the like), pteridinyl group (2-pteridinyl group and the like), phthalazinyl group (4-phthalazinyl group and the like), quinazolinyl group (2-quinazolinyl group, 4 -Quinazolinyl group), quinoxalinyl group (2-quinoxalinyl group, 3-quinoxalinyl group, etc.), indolizinyl group (2-indolidinyl group, etc.), benzoxazinyl group (2H-1,3-benzoxazin-2-yl group) ), Phenothiazinyl group (2
-Phenothiazinyl group, 3-phenothiazinyl group, etc.), phenazinyl group (2-phenazinyl group, 3-phenazinyl group etc.), phenoxazinyl group (2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group etc.) and the like. To be Preferred examples of the heterocyclic group include a 5-membered nitrogen-containing heterocyclic group, and among them, a thiazolyl group is most preferable.

[0026] As a group which may be substituted on the heterocyclic ring, for example, _{C 1-4 alkyl, C 1 -4} alkoxy, and halogen. Examples _of the _{C 1-4} alkyl such as methyl, ethyl, n- Examples include propyl, isopropyl, butyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. As C _1-4 alkoxy,
For example, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, n-butoxy, isobutoxy, sec
-Butoxy, tert-butoxy and the like can be mentioned, and halogen can include fluoro, chloro, bromo and the like. Other examples include a hydroxyl group, an amino group and a mercapto group. The number of the substituents may be 1 to 3.

The benzimidazole compound represented by the above formula (2) is a salt thereof, for example, an inorganic acid salt such as hydrochloride, nitrate or phosphate, or an organic acid such as paratoluene sulfonate or methyl sulfonate. A salt, a salt with an aromatic amine such as ammonia, ethylenediamine or 1,6-hexamethylenediamine and a salt with an alkali metal such as sodium or potassium may be used. Specific examples of the benzimidazole compound represented by the above formula (2) and salts thereof include, for example, methyl 2-benzimidazole carbamate (hereinafter abbreviated as MBC), ethyl 2-benzimidazole carbamate, 2- (4-
Thiazolyl) benzimidazole, methyl 2-benzimidazole carbamate hydrochloride, ethyl 2-benzimidazole carbamate hydrochloride, 2- (4-thiazolyl) benzimidazole hydrochloride, methyl 2-benzimidazole carbamate p-toluenesulfonic acid Examples thereof include salts, ethyl 2-benzimidazole carbamate p-toluenesulfonate, and 2- (4-thiazolyl) benzimidazole p-toluenesulfonate. MBC hydrochloride is preferably used.

The benzimidazole compound used in the present invention can be produced by a known technique, but a commercially available product may be used. Examples of commercially available products include Preventol BCM (trade name) (methyl 2-benzimidazole carbamate 98% by weight, manufactured by Bayer), M
Examples include BC hydrochloride (trade name) (MBC hydrochloride 98% by weight, manufactured by Yoshitomi Fine Chemical).

Examples of the isothiazoline compounds used in the present invention include compounds represented by the general formula (3).

[Chemical 9] (In the formula, R ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and R ₂ and R ₃ are the same or different and represent a hydrogen atom or a halogen atom.) Substitution represented by R ₁ in the above formula Examples of the hydrocarbon group in the optionally substituted hydrocarbon group are the same as those defined for Y ₁ above. The same thing can be mentioned as a preferable hydrocarbon group. Examples of the substituent of the optionally substituted hydrocarbon group represented by R ₁ include the same as those exemplified for Y ₁ . The preferable substituents are also the same.

Specific examples of the isothiazoline compound represented by the general formula (3) include 2-n-octyl-4-isothiazolin-3-one (hereinafter abbreviated as OIT), 5-
Chloro-2-methyl-4-isothiazolin-3-one,
5-chloro-2-n-octyl-4-isothiazoline-
3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4
-Isothiazolin-3-one and the like. These isothiazoline compounds may be used alone or in combination of two or more, and OIT is preferably used.

The isothiazoline compound used in the present invention can be produced by a known technique, but a commercially available product may be used. Examples of commercially available products include Skene 893T (trade name) (2-n-octyl-4-isothiazolin-3-one 98% by weight, manufactured by Rohm and Haas).

The industrial bactericidal composition of the present invention contains about 1 to 400 parts by weight of benzimidazole, preferably about 5 to 15 parts by weight, based on 100 parts by weight of the benzisothiazoline compound.
It may be contained at a ratio of about 0 parts by weight. Further, the industrial bactericidal composition of the present invention may further contain an isothizoline compound as a bactericidal effect enhancer. In this case, about 100 parts by weight of the benzisothiazoline compound, about 1 to 400 parts by weight of the benzimidazole compound and about 1 to 200 parts by weight of the isothiazoline compound, preferably about 100 parts by weight of the benzisothiazoline compound, benzimidazole. About 5 to 150 compounds
Parts by weight and about 2 to 150 isothiazoline compounds
It suffices if it is contained in a ratio of about parts by weight.

A solvent is preferably used for blending the above compounds, but the solvent is not particularly limited as long as it can dissolve or disperse these compounds. Examples of such a solvent include water, methanol,
Ethanol, n-propanol, iso-propanol,
n-butanol, tert-butanol, 3-methyl-3-
Alcoholic solvents such as methoxybutanol, such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, glycol solvents such as tripropylene glycol monomethyl ether, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as propylene carbonate, such as dioxane , Ether solvents such as tetrahydrofuran and ethyl ether, for example, ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate and dimethyl succinate. A solvent such as benzene,
Aromatic solvents such as toluene, xylene, methylnaphthalene, dimethylnaphthalene, isopropylnaphthalene, diisopropylnaphthalene, ethylbiphenyl, diethylbiphenyl and solvent naphtha, for example carbon tetrachloride,
Halogenated hydrocarbon solvents such as chloroform and methylene chloride, such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, N-
Examples thereof include polar solvents such as methylpyrrolidone.

Further, an industrially used aliphatic petroleum solvent or aromatic petroleum solvent may be used. Examples of the aliphatic petroleum solvent include mineral spirits. As the aromatic petroleum solvent, commercially available products such as MSP (distillation range 90 to 120 ° C., specific gravity (1
5/4 ° C) 0.820 or more, mixed aniline point 26 ° C or less, aromatic content (volume%) 70 or more), Superzole 100 (distillation range 95 to 111 ° C, specific gravity (15/4 ° C))
0.825 or more, mixed aniline point 26 ° C, aromatic content (volume%) 75 or more), Pecazole ARO-80 (distillation range 104 to 123 ° C, specific gravity (15/4 ° C) 0.832
Above, mixed aniline point 26 ℃, aromatic content (volume%) 7
5.9), Swazol 100 (distillation range 106-116)
℃, specific gravity (15/4 ℃) 0.835 or more, mixed aniline point 24.6 ℃ or less, aromatic content (volume%) 76.4),
Swazol 200 (distillation range 132-144 ° C, specific gravity (15/4 ° C) 0.844, mixed aniline point 23.8)
℃, aromatic content (volume%) 80.9), MHS (distillation range 140-170 ℃, specific gravity (15/4 ℃) 0.86-
0.88, mixed aniline point 11-12 ° C, aromatic content (volume%) 98 or more), high arom 2S (distillation range 15
2 to 187 ° C., specific gravity (15/4 ° C.) 0.816, mixed aniline point 47 ° C. or lower, aromatic content (volume%) 45 to 5
5), Swazol 310 (distillation range 153-177 ° C.,
Specific gravity (15/4 ° C.) 0.817, mixed aniline point 43.
6 ° C., aromatic content (volume%) 51.0), Supersol 150 (distillation range 153-197 ° C., specific gravity (15/4)
℃) 0.815, mixed aniline point 21.5 ℃, aromatic content (volume%) 50 or more), Shoishi Hysol (distillation range 1
53-198 ° C, specific gravity (15.6 / 15.6 ° C) 0.8
18, aromatic content (volume%) 55), HAWS (distillation range 154-190 ° C, specific gravity (15/4 ° C) 0.822,
Aromatic content (volume%) 50), Superzole 1500
(Distillation range: 155 to 171 ° C, specific gravity (15/4 ° C))
869, mixed aniline point 14.6 ° C, aromatic content (volume%) 98 or more), Nisseki Hysol 100 (distillation range 15
5 to 180 ° C, specific gravity (15/4 ° C) 0.870 to 0.8
80, mixed aniline point 15 ° C. or lower, aromatic content (volume%) 99.0 or higher), Vegasol R-100 (distillation range 156 to 174 ° C., specific gravity (15/4 ° C.) 0.874, mixed aniline point 14 ° C. , Aromatic content (volume%) 96.
4), Solvesso 100 (distillation range 158-177 ° C,
Specific gravity (15/4 ℃) 0.870, Mixed aniline point 14
℃, aromatic content (volume%) 98.0), MSS (distillation range 158-180 ℃, specific gravity (15.6 / 15.6 ℃)
0.86 to 0.89, mixed aniline point 13 to 14 ° C, aromatic content (volume%) 98 or more), SHELLSOL A
(Distillation range 160 to 182 ° C, specific gravity (15/4 ° C))
873, aromatic content (volume%) 98), Swazol 10
00 (distillation range 162-176 ℃, specific gravity (15/4 ℃)
0.878, mixed aniline point 12.7 ° C, aromatic content (volume%) 99.7), Idemitsu Ipsol 100 (distillation range 162-179 ° C, specific gravity (15/4 ° C) 0.875,
Mixed aniline point 13.5 ° C, aromatic content (volume%) 9
9.5 or more), Shoishi Tokusan Hisol (distillation range 162 to 1)
80 ° C, specific gravity (15/4 ° C) 0.881, mixed aniline point 12.6 ° C, aromatic content (volume%) 99.99), Swazol 1500 (distillation range 180-207 ° C, specific gravity (15/4 ° C) ) 0.886, mixed aniline point 16.5
℃, aromatic content (volume%) 98.8), Nisseki Hysol 150 (distillation range 182 to 216 ℃, specific gravity (15/4
C.) 0.887 to 0.904, mixed aniline point 17 ° C. or lower, aromatic content (volume%) 99.0 or higher), Supersol 1800 (distillation range 183 to 208 ° C., specific gravity (15)
/ 4 ° C) 0.889, mixed aniline point 15.7 ° C, aromatic content (volume%) 99 or more), Solvesso 150 (distillation range 185-211 ° C, specific gravity (15/4 ° C) 0.89).
6, mixed aniline point 18.3 ℃, aromatic content (volume%)
97.3), Idemitsu Ipsol 150 (distillation range 186-
205 ° C, specific gravity (15.6 / 15.6 ° C) 0.895,
Mixed aniline point 15.2 ° C, aromatic content (volume%) 9
9.5 or more), SHELLSOL AB (distillation range 18
7-213 ° C, specific gravity (15/4 ° C) 0.894, aromatic content (volume%) 99.5), Pegasol R-150 (distillation range 191-212 ° C, specific gravity (15/4 ° C) 0.89
0, mixed aniline point 18 ° C, aromatic content (volume%) 9
7.2), Swazol 1800 (distillation range 197-23
7 ° C., specific gravity (15/4 ° C.) 0.940, mixed aniline point 14.0 ° C., aromatic content (volume%) 99.6) and the like. Of these, water and / or glycol solvents are preferable. These solvents may be used alone or in combination of two or more kinds. As the solvent, it is preferable to use water and / or a glycol solvent.

Further, the industrial bactericidal composition of the present invention has known additives such as other algae and / or fungicides, surfactants, antioxidants and light stabilizers depending on its purpose and use. A defoaming agent may be added.

Other algae and / or fungicides include organic compounds such as 3-iodo-2-propynyl-butyl-carbamate, diiodomethyl-p-tolylsulfone and p-chlorophenyl-3-iodopropargylformal. Iodine compounds, for example thiocarbamate compounds such as tetramethylthiuram disulfide,
Nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile, for example N- (fluorodichloromethylthio) -phthalimide and N- (fluorodichloromethylthio) -N, N'-dimethyl-N-phenyl- Haloalkylthio compounds such as sulfamide,
Pyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, for example pyrithione compounds such as zinc pyrithione and sodium pyrithione, such as 2- (4-thiocyanomethylthio) benzothiazole. Benzothiazole-based compounds, such as 3- (3,4-dichlorophenyl) -1,1
A urea compound such as dimethylurea, for example α-t-
Butyl-α (p-chlorophenylethyl) -1H-1,
2,4-triazole-1-ethanol (trade name tebuconazole), 1-[(2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl-methyl) -1H-1, 2,4-triazole (trade name: propiconazole), 1- [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl-methyl]
-1H-1,2,4-triazole (trade name azaconazole) and other triazole compounds, for example 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine and other triazine compounds, such as 3 , 3,4,4-Tetrachlorotetrahydrothiophene-1,1-dioxide and other thiophene compounds such as 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4 Examples thereof include oxathiazine compounds such as -oxide. These other algae and / or fungicides may be used alone or in combination of two or more. Further, the blending ratio of these is appropriately determined depending on the dosage form, purpose and use.

As the surface active agent, known surface active agents such as soaps, nonionic surface active agents, anionic surface active agents, cationic surface active agents, amphoteric surface active agents, polymer surface active agents, etc. Examples thereof include agents, preferably nonionic surfactants and anionic surfactants.

Examples of nonionic surfactants include polyoxyalkylene aryl phenyl ethers, polyoxyethylene nonyl phenyl ethers, and block copolymers of ethylene oxide and propylene oxide.

Examples of anionic surfactants include alkylbenzene sulfonic acid metal salts, alkylnaphthalene sulfonic acid metal salts, polycarboxylic acid type surfactants, dialkyl sulfosuccinic acid ester metal salts, polyoxyethylene distyrenated phenyl ether sulfate ammonium. Examples thereof include salts and ligninsulfonic acid metal salts. Examples of these metal salts include sodium salt, potassium salt, magnesium salt and the like.

As the antioxidant, for example, 2,6
-Di-t-butyl-4-methylphenol, 2,2'-
Phenol-based antioxidants such as methylenebis [4-methyl-6-t-butylphenol], for example, amine-based antioxidants such as alkyldiphenylamine and N, N′-di-s-butyl-p-phenylenediamine. .

These surfactants and antioxidants are
For example, in the case of a liquid agent, about 0.1 to 20 parts by weight is added to 100 parts by weight of the liquid agent. Examples of the light stabilizer include hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. Such light stabilizers are
For example, in the case of a liquid agent, about 0.1 to 10 parts by weight is added to 100 parts by weight of the liquid agent.

The industrial bactericidal composition of the present invention is a known agent such as a liquid agent (including a water suspension agent and an oil agent), a paste agent, a powder agent, a granule agent, a microcapsule, etc. depending on its purpose and use. It can be used by formulating into a mold.
Further, it may be prepared as an inclusion compound, or may be prepared by supporting it on montmorillonite (smectites) such as layered silicate, or by adsorbing it on clay, talc, silica or the like.

The composition of the present invention is preferably used under the condition of pH value of 7-11. When the manufactured composition of the present invention is added to an industrial product, the pH value of the industrial product is 7 to 1
If it is within the range of 1, it can be used without adjusting the pH itself. When the pH value of the above industrial product is 7 or less, a pH adjusting agent such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia, ammonia can be used to adjust the pH value to 7 to 11. By adding an appropriate amount of water, triethanolamine, dimethylamine, diethylamine, trimethylamine, triethylamine, triisopropanolamine, monoethanolamine, diethanolamine, diisopropanolamine, monoethanolamine, diethanolamine, diisopropanolamine, magnesium oxide, etc. It can be carried out. The pH value of the above industrial products is 11
It is above, in order to adjust this to pH value 7-11, p
It can be carried out by adding an appropriate amount of an H regulator, for example, hydrochloric acid, citric acid, nitric acid, sulfuric acid, trisodium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate. In addition, adjustment of the above-mentioned pH value is carried out by the above-mentioned acidic pH
Using a mixture of the adjusting agent and the above basic pH adjusting agent,
You may adjust pH.

The industrial bactericidal composition of the present invention obtained as described above can exhibit excellent effects as a controlling agent against bacteria, mold, yeast, algae and the like. Therefore, for example, pulp and paper mills, various industrial water such as cooling water circulation process, oil for metal processing such as cutting oil, casein, starch paste, glue, coated paper, coating liquid for paper, surface sizing agent, paint, Adhesive, synthetic rubber latex, printing ink,
Polyvinyl alcohol film, vinyl chloride film,
It can be effectively used for controlling harmful microorganisms in various industrial products such as plastic products, cement admixtures, sealing agents, and jointing agents. More specifically, for example, slime control agents in paper pulp mills and cooling water circulation processes, metalworking oils, casein, starch coating solutions, preservatives for resin products, paints, synthetic rubber latex, resins, inks, silicone sealing agents, etc. It is preferably used as an industrial bactericidal agent.

The amount of the industrial composition of the present invention to be added may be appropriately determined depending on the object of application, but it is about 10 to 10.
20000 mg (active ingredient) / kg (product), preferably about 50 to 10000 mg (active ingredient) / kg (product)
Is preferably used as the concentration of The active ingredient as used herein refers to a benzisothiazoline-based compound and a benzimidazole-based compound.

[0046]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples.

[Examples 1 to 5] Examples 1 to 5 were prepared in the proportions shown below, and each formulation was added to the coating composition to prepare a drug-containing coating (Use Example 1 to Use Example 3 and Comparative Examples 1 to 1). Example 3) was prepared.

Example 1 Emulgen P was added to 47.5 g of water.
I-20T (trade name) (polyoxyethylene nonylphenyl ether, manufactured by Kao) was added in an amount of 15 g, and Proxel Press Paste P6 (trade name) (1,2-benzisothiazolin-3-one 80% by weight) was added to the solution. (Made by Abyssia)
37.5 g was added and the T.I. Stir with K homodisper. The solution was pulverized with a planetary ball mill to obtain 100 g of a preparation.

Example 2 Water 77.5 g, Emulgen P
I-20T (trade name) (polyoxyethylene nonylphenyl ether, manufactured by Kao) 10 g and Proxel Press Paste P6 (trade name) (1,2-benzisothiazolin-3-one 80% by weight, manufactured by Avicia) 12.5 g Was subjected to the same operation as in Example 1 to obtain 100 g of a preparation.

Example 3 Water 88.9 g, Emulgen P
6 g of I-20T (trade name) (polyoxyethylene nonylphenyl ether, manufactured by Kao) and Preventol B
Example 1 5.1 g of CM (trade name) (methyl 2-benzimidazole carbamate 98% by weight, manufactured by Bayer)
Following the same procedure as above, 100 g of the preparation was obtained.

Example 4 40 g of methyl carbitol,
Water 43.8 g, Emulgen PI-20T (trade name) (polyoxyethylene nonylphenyl ether, manufactured by Kao) 6 g, Preventol BCM (trade name) (methyl 2-
Benzimidazole carbamate 98% by weight, made by Bayer 5.1 g and Skane 893T (trade name) (2-
5.1 g of n-octyl-4-isothiazolin-3-one (98% by weight, manufactured by Rohm and Haas) was subjected to the same operation as in Example 1 to obtain 100 g of a preparation.

Example 5 Bankish 100 (trade name) (Nn-butyl-2-benzisothiazoline-3)
-ON 95% by weight, manufactured by Abyssia) was dissolved in 89.5 g of ethylene glycol to obtain a preparation.

[Preparation of Paint] A paint is prepared by mixing the following components.
Manufactured. Paint weight% (Mill base) Water 3.4 Ethylene glycol 1.7 Dispersant 0.9 Wetting agent 0.1 Antifoam 0.4 Titanium white 22.5 (Let down) Emulsion 43.9 Film-forming aid 2.4 Antifoam 0.4 Thickener 10.0Water 14.3 100.0

As a dispersant, Orotan 850 (trade name)
(Polycarboxylic acid sodium salt, manufactured by Rohm and Haas Co.), and Triton CF-10 (trade name) as a wetting agent
(Alkyl ether sulphate, manufactured by Union Carbamate), Nopco 804 which is a mineral oil as an antifoaming agent
3-L (trade name) (mixture of polyethylene glycol-type non-ionized surfactant, manufactured by San Nopco Ltd.), Titanium JR-900 (trade name) as titanium white
(Rutile type titanium oxide, manufactured by Teika Co., Ltd.), Ultrasol C-62 (trade name) as emulsion (acrylic / styrene emulsion, manufactured by Ganz Kasei Co., Ltd.)
Preservative-free product, CS-12 (trade name) (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, manufactured by Chisso Co., Ltd.) as a film-forming aid, thickener A 2% by weight aqueous solution of SP-600 (trade name) (hydroxyethyl cellulose, manufactured by Daicel Corp.) was used as.

Each of the above-mentioned preparations (Examples 1 to 5) was added to the above-prepared coating material at the ratio shown in Table 1 to prepare drug-containing coating materials (Use Examples 1 to 3 and Comparative Examples 1 to 3). The values in Table 1 show the added amount (% by weight) of each formulation to the paint.

USE EXAMPLE 1 0.5 parts by weight of the preparation of Example 1, 0.5 parts by weight of the preparation of Example 3 and 100 parts by weight of the above-prepared coating composition were added to T.I. K. A drug content paint was prepared by stirring with a homodisper for 1 hour.

[Use Example 2] 0.5 parts by weight of the preparation of Example 2, 0.5 parts by weight of the preparation of Example 3 and 100 parts by weight of the above-prepared coating composition were added to T.I. K. A drug content paint was prepared by stirring with a homodisper for 1 hour.

[Use Example 3] 0.5 parts by weight of the preparation of Example 1, 0.5 parts by weight of the preparation of Preparation 4 and 100 parts by weight of the above-prepared coating composition were added to T.I. K. A drug content paint was prepared by stirring with a homodisper for 1 hour.

Comparative Example 1 1.0 part by weight of the preparation of Example 2 and 100 parts by weight of the above-prepared coating composition were added to T.I. K. A drug content paint was prepared by stirring with a homodisper for 1 hour.

Comparative Example 2 1.0 part by weight of the preparation of Example 3 and 100 parts by weight of the above-prepared coating composition were added to T.I. K. A drug content paint was prepared by stirring with a homodisper for 1 hour.

Comparative Example 3 1.0 part by weight of the preparation of Example 5 and 100 parts by weight of the above-prepared coating composition were applied to K. A drug content paint was prepared by stirring with a homodisper for 1 hour.

[0062]

[Table 1]

Test Example 1 Antibacterial Test by Film Adhesion Method As a test bacterium, Escherichia
coli.:IF03044), Staphylococcus aureus (IF03061), and these test bacteria were cultured in a normal broth liquid medium at 28 ° C.
Precultured for 18 hours. Then, use a turbidimeter to measure turbidity at 0.2.
(OD 660 nm) and dispersed in a 1/500 concentration Nutrient Broth medium to give a bacterial solution for inoculation. The drug-containing paint prepared in any one of Use Examples 1 to 3 was used. 2 filter paper (3cm x 3c
m) was applied on both sides and dried at room temperature for 24 hours to form a coating film (hereinafter referred to as test sample). 0.2 mL of the bacterial solution was dropped on the test sample, and a polyethylene film was covered thereon to bring the drug-containing paint and the bacterial solution into close contact with each other. Then, after culturing at a constant humidity and constant temperature of 33 ° C for 24 hours, 10 mL of sterilized water
It was washed out with and the viable cell count in the solution was measured using a broth agar medium. The results are shown in Table 2. In addition, as the initial bacterial count, the bacterial count of the inoculum bacterial solution dropped on the test sample was measured. The bacterial solution for inoculation was used as a blank.

[0064]

[Table 2] From the results of Table 2, it became clear that the industrial sterilization composition according to the present invention exhibits an excellent antibacterial action.

[Test Example 2] Antibacterial test by inhibition circle method As a test bacterium, Escherichia
coli.:IF03044) and Staphylococcus aureus (IF03061), these test bacteria were dispersed on a broth agar medium.
A test sample prepared in the same manner as in Test Example 1 was stuck on the agar medium and cultured at 33 ° C. for 18 hours, and then the inhibition width (mm) formed was measured. The results are shown in Table 3.

[0066]

[Table 3] From the results in Table 3, when the active ingredient is alone (Comparative Example 1
It was shown that the sample containing two kinds of active ingredients (Use Example 1 to Use Example 2) or three kinds (Use Example 3) had higher antibacterial effect than that of Comparative Example 3).

[Test Example 3] Antifungal Effect Test A test sample was prepared in the same manner as in Test Example 1. The glucose agar medium sterilized by an autoclave was poured into a Petri dish having a diameter of 9 cm, and the test sample was attached to the center of the solidified agar plate. Aspergillus
nigar: IFO6341), Cladosporium cladosporioides: I
FO6348), Penicillium citrinum (Penicill)
ium citrinum: IFO6352), Aureobasidium pullulans: IFO6
353), Gliocladium
Virens: IFO6355) mixed bacterial solution of 5 kinds was sprayed onto the test sample piece, and then static culture was carried out at 28 ° C. for 4 weeks.
The degree of mold growth on the test sample pieces was evaluated according to the following evaluation criteria, and the results are shown in Table 4. 1: The area of the developing part of hyphae observed in the inoculated part of the test sample or the test sample piece exceeds 1/3 of the total area. 2: The area of the hypha developing portion found in the inoculated portion of the test sample or the test sample piece does not exceed 1/3 of the total area. 3: No hyphal growth was observed in the inoculated part of the test sample or the test sample piece.

[0068]

[Table 4] From the results in Table 4, when the active ingredient is alone (Comparative Example 1
-Compared with Comparative Example 3), it can be seen that the sample containing 2 kinds (Use Example 1-Use Example 2) or 3 kinds (Use Example 3) of the active ingredient exhibits an excellent antifungal effect.

Test Example 4 Coating Film Discoloration Test When the industrial bactericidal composition according to the present invention is used in a product,
The discoloration of the coating film was examined. 1/2 surface of each test sample surface prepared in the same manner as in Test Example 1 was coated with 1N hydrochloric acid, and the other surface was air-dried for 24 hours as a control, and then the degree of discoloration was visually observed. The results are shown in Table 5.

[0070]

[Table 5] It can be seen that even a strongly acidic solution does not turn yellow.

[0071]

INDUSTRIAL APPLICABILITY The industrial bactericidal composition of the present invention has a broad antibacterial spectrum against, for example, bacteria, fungi, algae, yeasts, etc., and is dramatically superior to the case where each active ingredient is used alone. High antibacterial activity is shown against each microorganism. Due to this strong potency, the required preservative and fungicidal effect can be achieved with a small amount of use.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Junichi Miyake             2-17-85 Jusohonmachi, Yodogawa-ku, Osaka-shi, Osaka Prefecture             No. Takeda Pharmaceutical Co., Ltd.             In the knee F-term (reference) 4H011 AA02 AA03 BA06 BB10 BB13                       BC19 DD01 DH03

Claims (13)

[Claims] 1. An industrial bactericidal composition comprising a benzisothiazoline compound and a benzimidazole compound. 2. The industrial bactericidal composition according to claim 1, further comprising an isothiazoline compound as a bactericidal efficacy enhancer. 3. A benzisothiazoline compound is represented by the general formula (1); (In the formula, Y ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and the A ₁ ring represents an optionally substituted benzene ring). The industrial sterilizing composition according to. 4. The compound represented by the formula (1), wherein Y ₁ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the benzene ring represented by A ₁ ring is an unsubstituted benzene ring. Industrial sterilizing composition. 5. A benzisothiazoline compound is 1, 2
-The industrial bactericidal composition according to any one of claims 1 to 4, which is at least one of -benzisothiazolin-3-one and N-n-butyl-benzisothiazolin-3-one. 6. A benzimidazole-based compound has the general formula (2): (In the formula, A ₂ ring represents an optionally substituted benzene ring, Z is a group represented by —NHCOOR (in the formula, R represents a hydrogen atom or an alkyl group) or an optionally substituted group 5) Or a compound represented by a 6-membered nitrogen-containing heterocyclic group) or a salt thereof, the industrial bactericidal composition according to any one of claims 1 to 5. 7. An NHC which is Z in the formula (2), wherein the A ₂ ring is an unsubstituted benzene ring or a benzene ring substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms.
The industrial bactericidal composition according to claim 6, wherein R in OOR is a C _1-8 alkyl group or Z is a thiazolyl group. 8. A benzimidazole compound is methyl
The industrial germicidal composition according to any one of claims 1 to 7, which is at least one selected from the group consisting of 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate and 2- (4-thiazolyl) benzimidazole. 9. An isothiazoline compound represented by the general formula (3): (Wherein R ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and R ₂ and R ₃ are the same or different and represent a hydrogen atom or a halogen atom). Industrial sterilization composition in any one of 1-8. 10. R ₁ is a C _1-18 alkyl group, R ₁
The industrial bactericidal composition according to claim 9, wherein ₂ and R ₃ are the same or different and each is a hydrogen atom or a halogen atom. 11. An isothiazoline-based compound is 2-n-octyl-4-isothiazolin-3-one, 5-chloro-
2-Methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 2- Methyl-4-isothiazoline-3-
On and 4,5-dichloro-2-n-octyl-4-
The industrial sterilizing composition according to any one of claims 1 to 10, which is at least one selected from the group consisting of isothiazolin-3-ones. 12. The industrial sterilizing composition according to claim 1, which further contains water or / and a glycol solvent. 13. The industrial sterilizing composition according to any one of claims 1 to 12, which is used under conditions of pH value of 7 to 11.