JPH10298012A - Microbicide composition and control of microorganism - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition exhibiting a high microbicidal action even at a small dose and excellent in the durability of the effect by combining a specific N-substituted benzoisothiazoline compound with one or more other microbicides such as bactericides and fungicides. SOLUTION: This microbicide composition comprises (A) an N-substituted benzoylisothiazoline compound of the formula [R is a (substituted) hydrocarbon which may have a substituent on the benzene ring] and (B) one or more compounds having microbicidal actions, selected from ester compounds, amide compounds, alcohol compounds, guanidine compounds, heterocyclic carbamate compounds, heterocyclic compounds, etc., except the N-substituted benzoisothiazoline compound. The components A and B are preferably compounded in amounts of 1 pt.wt. and 0.01-2000 pts.wt., respectively. The composition can especially be applied to industrial water liable to cause slim troubles, etc. The composition is added in an amount of about 1-30000 ppm to water to be treated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to various obstacles caused by the propagation of microorganisms such as fungi, bacteria, yeasts and algae, for example, water and slime obstacles in the papermaking process and industrial cooling water, production lines of various factories, etc. Is useful in removing slime obstacles and other problems in slime control, slime control treatment in metalworking oil circulating fluid, textile oil circulating fluid, wastewater treatment systems, coolers, etc., and antiseptic and fungicide treatment in the fields of paints, adhesives, etc. The present invention relates to a microbicidal composition and a microbial control method useful for antialgal treatment.

[0002]

2. Description of the Related Art With the demand for industrial water, a recirculating water system is actively used. In using this recirculated water,
Controlling and suppressing the growth of microorganisms has become an important issue. In addition to industrial water, with the diversification of industrial materials, disasters due to the proliferation of microorganisms and disasters due to the occurrence of mold and algae are widespread. In particular, in the fields of white water, pulp slurry, industrial cooling water, metalworking lubricating oil, aqueous emulsion, paper, wood, plywood, glue, and fiber in the papermaking process, fungi, bacteria, fungi, yeast, and algae It is urgently necessary to take measures against slime problems and microbial disasters.

[0003] Specifically, for example, slime (mud-like fine solids) adheres to inner walls of conduits, liquid supply passages, and the like, particularly stagnant portions, for supplying cooling water for circulating pulp slurry during a papermaking process. Easy and often causes slime disorders. A wide variety of organisms such as bacteria, fungi and algae are involved in the generation of this slime. When the slime is mixed as a foreign matter in the pulp slurry, the quality of the product such as discoloration is deteriorated, and also the paper is cut off, which is a factor to hinder the continuous operation of the paper machine and greatly reduces the production efficiency. Therefore, unless microorganisms are reduced in a short period of time, the slime generated may cause the production to be stopped. Further, in industrial cooling water, slime damage due to fungi, bacteria, algae and the like is liable to occur, resulting in deterioration of water flow, blockage of pipes, reduction of heat exchange efficiency, and the like, thereby lowering cooling efficiency. Further, the paper industry,
BACKGROUND ART Synthetic resin emulsions and aqueous latexes used in the fields of paints, adhesives and the like are spoiled by microorganisms during storage, causing not only a change in viscosity and coloring, but also offensive odor. Further, for example, any coating agent containing starch paste used for a coating color for producing coated paper tends to rot. Further, if molds are generated in the sizing agent containing starch paste or the like, the supply nozzle is clogged, and continuous operation becomes difficult.

As industrial disinfectants for preventing or eliminating the generation of such microorganisms, disinfectants containing various compounds such as isothiazoline compounds, halocyanoacetamide compounds and bromonitro alcohol compounds have been proposed. (For example, Japanese Patent Publication No. 60-54281,
JP-A-60-84203, JP-A-61-8310
No. 5, JP-A-62-70301, JP-A-3-70301.
176407, JP-A-5-201810, etc.). However, even if these disinfectants are added, it is difficult to reduce the number of microorganisms in a short time. In addition, many of these bactericides have a narrow antibacterial spectrum width by themselves and are applicable only to a limited type of microorganisms. For example, isothiazoline-based drugs and rhodan-based drugs are inferior in fast-acting properties, and resistant bacteria are easily generated by long-term use. In addition, alcoholic drugs, haloacetamide drugs and dithiol drugs are generally faster than isothiazoline drugs and rhodan drugs, but still have a small bactericidal and antibacterial action. Moreover, even if multiple fungicides are combined,
It works only additively. Therefore, it is not possible to effectively remove a slime disorder or the like involving various microorganism groups. In particular, it is difficult to maintain a sterilizing or antibacterial effect for a long time.

On the other hand, N-butylbenzisothiazolin-3-one is also known as a fungicide. This N-butyl benzoisothiazolin-3-one can maintain a bactericidal or antibacterial and antifungal effect for a long time.
In addition, it has the advantage of low inhalation toxicity of volatile components, easy handling, and excellent photodegradability, so that it has little effect on the environment due to the residual in the natural world. Have.

However, when N-butylbenzisothiazolin-3-one is used alone, the fast-acting effect is inferior, and the bactericidal and antifungal effects (minimum growth inhibitory concentration) of N-butylbenzisothiazolin-3-one are different from those of microorganisms. Greatly fluctuates. Therefore, it is necessary to add N-butyl benzoisothiazolin-3-one at a high concentration in order to peel and destroy slime adhered to pipes and the like.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a microbicidal composition exhibiting high microbicidal activity even in a small amount, and a method for controlling microorganisms using the same. It is another object of the present invention to provide a microbicidal composition capable of maintaining a microbial control effect over a long period of time, and a microbial control method using the same. Still another object of the present invention is to provide a microbicidal composition which exhibits a broad bactericidal or antibacterial (antimicrobial) spectrum and which can effectively prevent damage due to the propagation of microorganisms, for example, slime damage due to slime generation, and the like. An object of the present invention is to provide a method for controlling microorganisms used. Another object of the present invention is to provide a method capable of effectively increasing the activity of various compounds having a microbicidal action by using a small amount of an active ingredient in combination.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that N-substituted benzoisothiazoline compounds can be used as other fungicides (or antibacterial agents), fungicides, algicides. N-substituted benzoisothiazoline-based compounds function as effective potency enhancers even in small amounts when combined with a microbicide such as an antimicrobial agent, and found that the activity of the microbicide is significantly improved, thus completing the present invention. did. That is, the microbicide composition of the present invention has the following formula (1)

[0009]

Embedded image (Wherein, R represents a hydrocarbon group which may have a substituent, and a benzene ring may have a substituent). And a non-N-substituted benzoisothiazoline compound having the formula:

The non-N-substituted benzoisothiazoline compounds include various compounds having a microbicidal action (for example, bactericidal or antibacterial, fungicidal, algicidal actions), for example, (1)
Ester compounds, (2) amide compounds, (3) alcohol compounds, (4) guanidine compounds, (5) heterocyclic carbamate compounds, (6) heterocyclic compounds, (7) non-heterocycles Group consisting of the formula organic sulfur compound, (8) quaternary ammonium salt compound, (9) aromatic nitrile compound, (10) phenol compound, (11) acetal compound and (12) organic arsenic compound. In many cases, at least one selected from the group consisting of:

The amount of the N-substituted benzoisothiazoline compound may be, for example, about 0.01 to 2000 parts by weight based on 1 part by weight of the non-N-substituted benzoisothiazoline compound.

In the method of the present invention, the microorganisms are controlled by adding the microbicidal composition to the liquid to be treated. In this method, the amount of the microbicide composition added may be about 1 to 30,000 ppm based on the liquid to be treated,
The addition amount of the N-substituted benzoisothiazoline compound may be about 1 to 20,000 ppm based on the liquid to be treated. The liquid to be treated is industrial water, papermaking process water, industrial cooling water, circulating liquid for industrial manufacturing equipment, industrial washing water, industrial oil, latex, coating liquid, paste, paint, printing ink,
An adhesive, a sizing agent, or the like may be used. The method of the present invention further includes a method of adding the N-substituted benzoisothiazoline compound to a microbicide to enhance the microbicidal action of the microbicide. In this specification,
The term “microorganism” is used to include bacteria, fungi, protozoa, single-celled algae, and also widely include multicellular algae. In addition, “microbicidal” and “microbial control” include not only the meaning of killing microorganisms or completely preventing their growth (or reproduction), but also the meaning of suppressing or preventing the growth (or reproduction) of microorganisms. . Further, the N-substituted benzoisothiazoline-based compound and the non-N-substituted benzoisothiazoline-based compound may be abbreviated as “NBIT-based compound” and “non-NBIT-based compound”, respectively.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the above formula (1), examples of the hydrocarbon group represented by R 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 methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Examples thereof include linear or branched alkyl groups having about 1 to 10 carbon atoms, such as s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, and decyl. Preferred alkyl groups include, for example, alkyl groups having about 1 to 6 carbon atoms (in particular, about 2 to 6 carbon atoms) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, and t-butyl. It is.
A particularly preferred alkyl group is, for example, an alkyl group having about 3 to 5 carbon atoms, especially a butyl group. Alkenyl groups include, for example, vinyl, allyl, isopropenyl, 1-
An alkenyl group having about 2 to 8 carbon atoms (particularly about 2 to 6 carbon atoms) such as propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, and 3-pentenyl is included. Preferred alkenyl groups are alkenyl groups having about 3 to 5 carbon atoms, especially alkenyl groups having 4 carbon atoms such as 2-butenyl. Examples of the alkynyl group include an alkynyl group having about 2 to 8 carbon atoms (particularly, about 2 to 6 carbon atoms) such as ethynyl, 2-propynyl, 2-butynyl, and 3-pentynyl. Preferred alkynyl groups are alkynyl groups having about 3 to 5 carbon atoms, especially alkynyl groups having 4 carbon atoms such as 2-butynyl. Examples of the cycloalkyl group include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
C3-C10 such as cycloheptyl and cyclooctyl
Cycloalkyl groups can be exemplified. Preferred cycloalkyl groups include, for example, cycloalkyl having about 5 to 7 carbon atoms, such as cyclopentyl and cyclohexyl. The aryl group includes, for example, an aryl group having about 6 to 14 carbon atoms, such as phenyl, naphthyl, and anthryl. Preferred aryl groups include, for example, aryl groups having about 6 to 10 carbon atoms, such as a phenyl group. The aralkyl group includes, for example, C _6-14 aryl-C such as benzyl, benzhydryl, phenethyl and phenylbutyl.
_1-4 alkyl groups and the like. Preferred aralkyl groups include a C _6-10 aryl-C _1-2 alkyl group such as a benzyl group.

The hydrocarbon group represented by R may have a substituent. Examples of the substituent of the hydrocarbon group include a halogen atom (fluorine, chlorine, bromine and iodine atom),
Haloalkyl group (for example, C _1-2 haloalkyl group such as chloromethyl, trifluoromethyl and the like), cyano group,
Nitro group, amino group, N-substituted amino group (for example, mono- or di-C such as dimethylamino, ethylamino, etc.)
_1-4 alkylamino group, etc.), hydroxyl group, alkoxy group (for example, C _1-4 alkoxy group such as methoxy, ethoxy, propoxy, butoxy, t-butoxy and the like), aryloxy group (for example, C group such as phenoxy and the like)
_6-10 aryloxy group, etc.), alkylthio group (eg, C _1-4 alkylthio group such as methylthio, ethylthio, etc.), arylthio group (eg, C _6-10 aryl group such as phenylthio, etc.), carboxyl group, alkoxycarbonyl Group (for example, C _1-4 alkoxy-carbonyl group such as methoxycarbonyl, ethoxycarbonyl and the like), acyl group (for example, C.sub.4 such as formyl and acetyl).
_1-6 acyl group). When the hydrocarbon group is an aryl group or an aralkyl group, the aromatic ring may be substituted with an alkyl group (for example, a C _1-4 alkyl group such as methyl and ethyl). These substituents may be the same or different and may substitute 1 to 5, preferably 1 to 3 hydrocarbon groups.

Preferred hydrocarbon groups represented by R include, for example, aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups, and cycloalkyl groups.
About 6 aliphatic hydrocarbon groups (particularly, C _1-6 alkyl groups and C _2-6 alkenyl groups) are preferred. Above all, R
Is preferably a C _1-6 alkyl group, especially a C _3-5 alkyl group, especially a butyl group.

In the above formula (1), the benzene ring may have a substituent. Examples of such a substituent include a substituent which the hydrocarbon group represented by R may have. Preferred substituents that the benzene ring may have include, for example, the halogen atom, C _1-4
Examples include an alkyl group, a hydroxyl group and a C _1-4 alkoxy group. These substituents are added to the benzene ring by 1 to 4
, Preferably about 1-2. In a preferred compound, the benzene ring is unsubstituted.

Specific examples of preferred compounds represented by the above formula (1) include N-methylbenzisothiazoline-3
-One, N-ethylbenzisothiazolin-3-one,
N-propyl benzoisothiazolin-3-one, N-butyl benzoisothiazolin-3-one (BBIT), N
-Isobutyl benzoisothiazolin-3-one, N-pentyl benzoisothiazolin-3-one, N-isopentyl benzoisothiazolin-3-one, N-hexyl benzoisothiazolin-3-one, N-allyl benzoisothiazolin-3-one, N- (2-butenyl) benzoisothiazolin-3-one and the like. Among them, N
-Butylbenzisothiazolin-3-one (BBIT)
Is often used. The compounds represented by the formula (1) can be used alone or in combination of two or more.

A feature of the present invention resides in that the activity of a non-NBIT compound having a microbicidal action is greatly improved by combining it with an NBIT compound, and the durability is enhanced. That is, the NBIT-based compound seems to function as an efficacy enhancer or a control promoter for non-NBIT-based compounds. Therefore, even if the addition amount of the NBIT compound is extremely small, the microbial control activity (efficacy) and control efficiency of the non-NBIT compound are greatly improved, and a broad bactericidal or antibacterial (antimicrobial) spectrum is exhibited. Growth and reproduction of various microorganisms can be suppressed. And
With a small amount of the microbicide composition, a high microbial control effect can be maintained for a long time.

The type of non-NBIT compound is not particularly limited as long as it has a microbicidal activity, and a wide range of fungicides or antibacterials, fungicides, algicides and the like can be used. Examples of the non-NBIT compound include (1) ester compounds, (2) amide compounds, (3) alcohol compounds, (4) guanidine compounds, (5) non-heterocyclic carbamate compounds, ( 6) heterocyclic compounds, (7) non-heterocyclic organic sulfur compounds, (8) quaternary ammonium salt compounds, (9) aromatic nitrile compounds, (10)
Phenol compounds, (11) acetal compounds, and (12) organic arsenic compounds.

(1) Examples of the ester compound include bis-1,4-bromoacetoxy-2-butene (BBA).
Halo fatty acid ester compounds such as B); and halogen-containing unsaturated carboxylic acid ester compounds such as diethyl monochlorofumarate and diethyl monobromofumarate. (2) The amide compound includes, for example, 2,2-dibromo-3-nitrilopropanamide,
Bromoacetamide compounds such as 2,2-dibromo-3-nitrilo-N-methylpropanamide and halo fatty acid amide compounds such as iodoacetamide compounds such as iodoacetamide are included. (3) Examples of the alcohol compound include 2,2-dibromo-2-nitroethanol (DBNE) and 2-bromo-2-nitropropane-
Nitro group-containing alcohol compounds such as 1,3-diol (BNPD) and 2-hydroxymethyl-2-nitro-1,3-propanediol; 2-hydroxymethylamino-2-methylpropanol (HMAMP), 2-hydroxymethyl Amino alcohol compounds such as aminoethanol (HMAE); haloallyl alcohol compounds such as 2,3,3-triiodoallyl alcohol; (4) Non-heterocyclic carbamate compounds include:
For example, an alkyl carbamate compound such as 3-iodo-2-propynylbutyl carbamate (IPBC) and the like can be mentioned. (5) Examples of the guanidine compound include dodecylguanidine hydrochloride, dodecylguanidine hydrobromide, decylguanidine hydrochloride, 1,1'-hexamethylenebis [5
-(4-chlorophenyl) biguanide] dihydrochloride and the like.

(6) Examples of the heterocyclic compound include oxygen, sulfur and nitrogen atoms (particularly sulfur-containing heterocyclic compounds such as sulfur-containing heterocyclic compounds and nitrogen-containing heterocyclic compounds (excluding sulfur-containing heterocyclic compounds)). And about 3 to 8 members (particularly 5 to 6 members) containing at least one hetero atom selected from
And the like, and heterocyclic compounds having a heterocycle (including condensed heterocyclic compounds). Examples of the sulfur-containing heterocyclic compound include halogenated dithiol compounds such as 4,5-dichloro-1,2-dithiol-3-one and 4,5-dibromo-1,2-dithiol-3-one;
3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide, 3,3,4-trichlorotetrahydrothiophen-1,1-dioxide, 3,3-dichlorotetrahydrothiophen-1,1-dioxide and the like Tetrahydrothiophene compounds; benzothiazole compounds such as 2- (4-thiocyanomethylthio) benzothiazole (TCMTB); benzoisothiazoline compounds such as 1,2-benzoisothiazolin-3-one (BIT); 2-methyl-4-isothiazoline -3-one (M
IT), 5-chloro-2-methyl-4-isothiazolin-3-one, 4,5-dichloro-4-isothiazoline-
3-one (Cl-MIT), 4,5-dichloro-2-octyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one (OIT), 2-methyl-4,5- Trimethylene-4-isothiazoline-3-
Isothiazoline compounds such as on (MTI); 3,5-
Examples thereof include thiadiazine compounds such as dimethyl-tetrahydro-1,3,5-2H-thiadiazine-2-thione. Examples of the nitrogen-containing heterocyclic compound include hexahydro-1,3,5-tris (2-hydroxyethyl) -s-
Triazine compounds such as triazine; 2,3,5,6-
Halopyridine compounds such as tetrachloro-4- (methylsulfonyl) pyridine and zinc pyrithione (ZP
T), pyridine compounds such as pyrithione compounds such as sodium pyrithione; and benzimidazole compounds such as methyl-2-benzimidazole carbamate (MBC) and 2- (4-thiazolyl) benzimidazole.

(7) Non-heterocyclic organic sulfur compounds include:
For example, rhodan compounds such as methylenebisthiocyanate (MBTC); dithiocarbamate compounds such as ethylenethiuram monosulfide and tetramethylthiuram disulfide; N- (fluorodichloromethylthio) phthalimide, N- (dichlorofluoromethylthio) -N Haloalkylthio compounds such as', N'-dimethyl-N-phenyl-N-phenylsulfamide; and sulfone compounds such as diiodomethyl-p-tolylsulfone. (8) The quaternary ammonium salt compounds include, for example, benzalkonium chloride, didecyldimethylammonium chloride and the like.
(9) As the aromatic nitrile compound, for example, 2,
4,5,6-tetrachloroisophthalonitrile and the like can be exemplified. (10) Examples of the phenolic compound include o-phenyl-phenol and p-chlorometaxylenol. (11) Acetal compounds include, for example, p-chlorophenyl-3-iodopropargyl formal. (12) Organic arsenic compounds include, for example, 10,10'-oxybis-10
H-phenoxyarsine and the like. These non-NBIT compounds can be used alone or in combination of two or more.

Preferred non-NBIT compounds include, for example, (1) ester compounds (eg, halo fatty acid ester compounds) and (2) amide compounds (eg,
Halo fatty acid amide compounds, etc.), (3) alcohol compounds (eg, nitro group-containing alcohol compounds, amino alcohol compounds, etc.), (4) non-heterocyclic carbamates (eg, alkyl carbamate compounds, etc.),
(5) guanidine compounds, (6) heterocyclic compounds (for example, sulfur-containing heterocyclic compounds such as dithiol compounds, thiophene compounds, and benzothiazole compounds; nitrogen-containing heterocyclic compounds such as triazine compounds, pyridine compounds, and benzimidazole compounds) Compound) and the like.

The microbicidal composition comprising the NBIT compound and the non-NBIT compound, wherein the NB
Even a small amount of the IT compound enhances the microbicidal activity (microbial control activity) of the non-NBIT compound. Therefore, the proportion of each component can be selected in a wide range that does not impair the microbicidal activity such as sterilization or antibacterial, antifungal, and antialgal activities according to the type of the non-NBIT compound. For example, the ratio of the NBIT compound is , 0.01 to 1 part by weight of the non-NBIT compound
2,000 parts by weight, preferably 0.1-1000 parts by weight, more preferably 0.2-500 parts by weight (for example, 0.2-100 parts by weight), especially about 0.3-50 parts by weight. In particular, when the non-NBIT compound is a halofatty acid amide compound, a nitro group-containing alcohol compound or a guanidine compound, the ratio of the NBIT compound is 10 to 100 parts by weight based on 1 part by weight of the non-NBIT compound.
It is often about 0 parts by weight. When used for fungicide, the ratio of NBIT-based compounds is
By setting the amount to, for example, 0.1 to 10 parts by weight, preferably about 0.2 to 5 parts by weight with respect to 1 part by weight of the system compound, a high control action against a wide range of mold can be exhibited, and also a synergistic effect can be obtained. In many cases, a strong antifungal effect can be obtained.

The form of the microbicidal composition of the present invention may be an NBIT compound represented by the above formula (1) and a non-NBI compound.
There is no particular limitation as long as it contains a T-based compound.
Granules, powders, granules, fine powders, pastes, sprays and the like may be used, and they may be used as liquids such as emulsions, wettable powders, aqueous solvents and suspensions. Examples of solid carriers in powders and the like include clays such as kaolin, bentonite, and acid clay, talcs, silicas, alumina, activated carbon, and the like. One or more of these solid carriers can be used.

As the solvent (liquid carrier) in the liquid preparation,
Various solvents capable of dissolving or dispersing the active ingredient, for example, water and / or an organic solvent can be used. The solvent may be water alone, or may be used as a mixed solvent of water and an organic solvent. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, and butyl alcohol; esters such as methyl acetate and ethyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride; ethers such as dioxane and tetrahydrofuran; polar solvents such as dimethylformamide, dimethylsulfoxide and acetonitrile; ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol; Tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanedio , And the like polyhydric alcohols and derivatives thereof such as glycerin. Derivatives of polyhydric alcohols include glycol solvents such as cellosolves such as ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve); diethylene glycol monomethyl ether, diethylene glycol Examples include carbitols such as monoethyl ether, and tripropylene glycol monomethyl ether. These solvents can be used alone or in combination of two or more. Preferred solvents include hydrophilic organic solvents (particularly water-soluble organic solvents) such as water, alcohols, polyhydric alcohols and derivatives thereof. Preferred polyhydric alcohols and derivatives thereof include, for example, glycols (eg, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc.), cellosolves (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), Carbitols (eg, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc.)
Is included.

When water and an organic solvent are used as a mixed solvent, the ratio of water to the organic solvent can be selected within a range that does not impair the activity and stability of the NBIT compound and the non-NBIT compound. Water / organic solvent = 5 / 95-
95/5 (weight ratio), preferably 10/90 to 90/1
0 (weight ratio), more preferably 25/75 to 75/2
It is about 5 (weight ratio).

The total content of the NBIT compound and the non-NBIT compound in the microbicidal composition can be selected in consideration of handling properties and the like within a range that does not impair bactericidal or antibacterial, fungicidal or algicidal activities. For example, in the case of a liquid preparation, 1 to 90% by weight,
Preferably, it is about 2 to 50% by weight.

The microbicidal composition may contain various additives, for example, a surfactant, depending on the purpose, use and the like.
Antioxidants, carboxymethylcellulose, alginic acid and its salts, polymers such as polyvinyl alcohol, auxiliaries such as rust inhibitors, bentonite, vegetable oils, insecticides, fragrances and the like may be added. When a microbicide is used as a liquid agent such as an emulsion among these additives, a surfactant is often used.

As the surfactant, soaps, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants and the like can be used. These surfactants can be used alone or in combination of two or more. Preferred surfactants include nonionic surfactants and anionic surfactants. Examples of the nonionic surfactant include polyoxyalkylene aryl phenyl ether, polyoxyethylene nonyl phenyl ether, fatty acid polyhydric alcohol ester, fatty acid polyhydric alcohol polyoxyethylene ether, fatty acid sucrose ester, ethylene oxide and propylene oxide. And the like. Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl naphthalene sulfonate, α-olefin sulfonate, polycarboxylic acid and salts thereof, dialkyl 2-sulfosuccinate, and polyoxyethylene distyrenated phenyl ether. Sulfate salt, lignin sulfonate, lignin sulfonate and the like can be mentioned. Examples of the salt include an alkali metal salt such as an ammonium salt, a sodium salt, and a potassium salt. The type of the antioxidant is not particularly limited, and examples thereof include phenol-based oxidations such as 2,6-di-t-butyl-4-methylphenol and 2,2′-methylenebis [4-methyl-6-t-butylphenol]. Inhibitor, alkyl diphenylamine, N,
Examples include amine antioxidants such as N'-di-s-butyl-p-phenylenediamine. The amount of the surfactant and the antioxidant used is, for example, 0.01 to 10% by weight, and preferably about 0.1 to 5% by weight, respectively, in many cases in the case of a liquid.

Microbicidal compositions as tablets, granules, powders, granules, fine powders, pastes, sprays, and solutions can be prepared by conventional methods. For example, the liquid preparation can be prepared by stirring and mixing the component and the solvent together with a surfactant and other additives as necessary.

In the method of the present invention, the use of the above-mentioned NBIT compound can significantly improve the microbicidal activity of the non-NBIT compound such as bactericidal (or antibacterial), fungicidal and algicidal activities. Therefore, when the microbicidal composition is added to the liquid to be treated, the liquid to be treated can be effectively subjected to microbicidal treatment. In particular, in such a method, even if the amount of the microbicidal composition added to the liquid to be treated is small, a high microbial control action is exhibited, and a high microbicidal activity is maintained for a long time. The amount of the microbicide composition added to the liquid to be treated can be selected from a wide range depending on the type of the liquid to be treated, the degree of contamination, and the like, and is usually 1 to 30,000 ppm (for example, 1 to 10000 ppm), preferably 5 to 5000 ppm.
ppm (for example, 10 to 4000 ppm), more preferably 10 to 2000 ppm (for example, 20 to 1000 ppm).
ppm), and often about 50 to 500 ppm. In addition, when the microbicidal composition is added to the liquid to be treated in an amount of 10 to 1000 ppm, especially about 10 to 500 ppm, a high microbicidal effect is effectively exhibited in most cases. More specifically, for example, when used as a slime control agent for papermaking, the amount of the microbicide composition added to white water or pulp slurry is, for example, 1
It is about 0 to 200 ppm (preferably 10 to 100 ppm), and when it is added to cooling water as circulating water to suppress slime generation or prevent algae from growing, the microbicide composition is added to the amount of water retained. The amount is, for example,
It is about 5 to 200 ppm (preferably 10 to 100 ppm).

The amount of the NBIT compound to be added can also be selected according to the type of the liquid to be treated, the type of the non-NBIT compound, and the like.
m (for example, 1 to 10000 ppm), preferably 5 to
3000 ppm (for example, 10 to 2000 ppm), more preferably 10 to 1000 ppm (for example, 20 to 20 ppm)
500 ppm), and often about 50 to 250 ppm. The NBIT compound is, for example, 10 to 500 ppm, preferably 10 ppm, based on the liquid to be treated.
Addition of about 250 ppm can significantly increase the microbicidal activity of the non-NBIT compound, and can greatly reduce the amount of the entire microbicide used.

In the method for controlling microorganisms, the addition method is not particularly limited, and a mixture obtained by mixing an NBIT compound and a non-NBIT compound at a predetermined ratio may be added to the liquid to be treated. The non-NBIT compound may be added separately to a predetermined concentration.

The microbicidal compositions of the present invention exhibit a broad bactericidal or antibacterial (antimicrobial) spectrum and provide fungi, bacteria,
Various disorders (such as slime disorders) due to propagation of microorganisms such as yeasts and algae can be effectively and reliably prevented. Therefore, the microbicidal composition of the present invention can be applied to various liquids to be treated, and can be used in aqueous treatment liquids, for example, white water or pulp slurry in the papermaking process (papermaking process water), industrial cooling water, industrial washing water. , Circulating water, lubricating oils for metalworking, aqueous emulsions, aqueous coating agents and treating agents for paper, wood, plywood, etc., sizing agents (starch slurry etc.), industrial treating liquids such as aqueous treating agents for textile processing, It can be applied to household liquids. Industrial water particularly susceptible to slime damage [for example, papermaking white water or pulp slurry in the paper process (papermaking process water), circulating fluid for industrial manufacturing equipment (eg,
Circulating fluid for cooling tower, circulating fluid for metalworking, circulating fluid for fiber spinning oil, circulating fluid for coating color), industrial cooling water such as cooling water for cooling tower, industrial water, cooling water for cooling and heating, etc.] Applied. In particular, when added to papermaking white water or slurry, circulating water that is repeatedly circulated and used, the growth and propagation of microorganisms can be significantly suppressed,
It is effective in controlling slime generation.

A microbicidal composition may be directly added to synthetic resin emulsions, latex, starch paste, glue, cutting oil, industrial oils (metal working oils, fiber oils, etc.), or the like. The microbicide composition may be added to a secondary product such as a coating liquid (such as a coating color), a paint (such as a paint or an antifouling paint), a printing ink, an adhesive, or a sizing agent. Furthermore, the microbicidal composition is used for disinfecting cosmetics, non-woven fabrics, leather, etc., fungicide, anti-algae treatment, food plants, sanitization of floors and walls of facilities where hygiene is required such as hospitals, It is also useful for fungicide treatment.

[0038]

According to the microbicidal composition and the method for controlling microorganisms of the present invention, since the above-mentioned NBIT compound and non-NBIT compound are combined, high microbicidal activity can be exhibited even in a small amount. In addition, the number of microorganisms in the water to be treated is significantly reduced, and the effect of controlling microorganisms can be maintained for a long time. Further, by the combination of the components,
It exhibits activity against a wide range of microorganisms, and can effectively prevent obstacles due to propagation of microorganisms, such as slime damage due to slime generation. In the method of the present invention, the non-NB
Combination with an IT-based compound can effectively enhance the bactericidal or antibacterial, fungicidal, and algicidal activities of the non-NBIT-based compound. Therefore, even if it is added in a small amount, it can be controlled quickly and various obstacles due to propagation of microorganisms can be effectively prevented. Further, the amount of the microbicide used can be reduced, and the liquid to be treated can be efficiently treated due to the strong microbicidal activity.

[0039]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. Examples 1 to 10 and Comparative Examples 1 to 10 The following tests were performed to examine the sterilization of a cooling tower cooling water in a model system. The following NBIT compound (hereinafter, referred to as A component) and / or the following non-NBIT compound
System compound (hereinafter referred to as B component) using sterile water,
The solution was diluted to a predetermined concentration shown in the table to prepare a diluted drug solution (20 ml). The concentration of each component in the table is based on the amount (pp
m). A1 component: N-butylbenzisothiazolin-3-one (BBIT, content 90.0% by weight) B1 component: bis-1,4-bromoacetoxy-2-butene (BBAB, content 90.0% by weight) B2 component: 4,5- Dichloro-1,2-dithiol-3
-One (RYH-86, content 97.0% by weight) B3 component: 2-bromo-2-nitropropane-1,3-
Diol (BNPD, content 97.0% by weight) B4 component: 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (TeCS, content 98.0% by weight) B5 component: 2,2-dibromo-2-nitro Ethanol (D
BNE, content: 75.8% by weight) B6 component: hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine (HTHE-triazine,
B7 component: 2-hydroxymethylamino-2-methylpropanol (HMAMP, content 90.0% by weight) B8 component: 1,1'-hexamethylenebis [5- (4-
Chlorophenyl) biguanide] dihydrochloride (chlorhexidine, content 100% by weight) B9 component: 2,2-dibromonitrilopropionamide (DBNPA, content 95.0% by weight) B10 component: 2-hydroxymethylaminoethanol (HM
(AE, content 97.0% by weight) On the other hand, the following five test bacteria were inoculated into a GB medium,
C. for 18 hours with shaking culture (pre-culture) and O.D. D. Dilute to 0.20 at 660 nm and mix in equal amounts,
A mixed bacterial solution was prepared. Pseudomonas aerugin
osa) IFO 3080 (-) Serratia marcescens IFO 37
35 (-) Flavobacterium suvolens
avolens) ATTC 958 (-) Alcaligenes faecali
s) IFO 13111 (-) Staphylococcus aureus
reus) IFO 12732 (+) Then, 0.1 ml of the above bacterial solution (about 10 ^{8 in} total number of bacteria in the mixed solution) was added to 20 ml of the drug solution, and the number of bacteria after 24 hours of contact was examined. 1 to Table 10 were obtained. The number of bacteria was measured in the same manner as described above, using sterile water containing no drug as a blank in place of the drug solution.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

[0049]

[Table 10] As is clear from Tables 1 to 10, when the A component and the B component are combined, the number of bacteria can be significantly reduced synergistically as compared with the comparative examples using the A component and the B component alone.

Examples 11 to 13 and Comparative Examples 11 to 13 The following tests were conducted to examine the control activity against microorganisms.

The following NBIT compound (hereinafter referred to as A component) and / or the following non-NBIT compound (hereinafter B)
) Was diluted with sterile water in the proportions shown in the table to prepare a drug solution having an active ingredient content of 10% by weight in total.

A 1 component: N-butylbenzisothiazolin-3-one (BBIT, content 90.0% by weight) B11 component: 2,3,5,6-tetrachloro-4-methylsulfonylpyridine (Densyl S-100, content B12 component: zinc bis (2-pyridylthio-1-oxide) (ZPT, content 50% by weight) B13 component: 2- (4-thiocyanomethylthio) benzothiazole (TCMTB, content 20% by weight) The following test was conducted to examine the antibacterial activity of fungi against fungi. After culturing at 28 ° C. for 3 days using a glucose broth agar medium containing the above-mentioned drug solution at a predetermined ratio by a multiple dilution streaking method, the presence or absence of growth of the test bacteria was visually observed, and the minimum growth inhibitory concentration (MIC, μg / μg / mL). Table 11 shows the results.

Mold (a) Aspergillus niger (b) Penicillium citrinu
m)

[0054]

[Table 11] As is clear from Table 11, when the A component and the B component are combined, the growth inhibitory action against mold can be synergistically increased as compared with the comparative example using the A component and the B component alone.

Examples 14 to 15 and Comparative Examples 14 to 15 Example 11 was repeated except that the following compounds were used as the non-NBIT compound (component B) and the following molds were used as microorganisms in addition to the above molds: To 13 and Comparative Examples 11 to
The same operation as in Example 13 was performed, and the control activity against microorganisms was examined. Table 12 shows the results.

B14 component: 3-iodo-2-propynylbutylcarbamate (IPBC, content 100% by weight) B4 component: 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (TcCS, content 10 Wt%) Mold (c) Cladosporium Cladosporioides (Clados
porium cladosporioides) (d) Mucor spinescens

[0057]

[Table 12] As is clear from Table 12, when the A component and the B component are combined, the growth inhibitory action against mold can be synergistically increased as compared with the comparative example using the A component and the B component alone.

Example 16 and Comparative Example 16 The following compounds were used as the non-NBIT compound (component B), and the following yeasts were used as microorganisms in addition to the above-mentioned molds. Example 14-
The same operation as in Example 15 was performed, and the control activity against microorganisms was examined. Table 13 shows the results.

B15 component: Methyl-2-benzimidazole carbamate (MBC, content: 10% by weight) Yeast (e) Rhodotorula rubra (f) Saccharomyces cerevisiae
visiae)

[0060]

[Table 13] As is clear from Table 13, when the A component and the B component are combined, the growth inhibitory action against mold can be increased synergistically, and the amount of A Even if present, it exerts a controlling effect on a wide range of fungi.

Claims (10)

[Claims] [Claim 1] The following formula (1) (Wherein, R represents a hydrocarbon group which may have a substituent, and a benzene ring may have a substituent). And a non-N-substituted benzoisothiazoline compound having the following formula: 2. The non-N-substituted benzoisothiazoline-based compound includes (1) an ester-based compound, (2) an amide-based compound, (3) an alcohol-based compound, (4) a guanidine-based compound, and (5) a non-heterocyclic compound. Carbamate compounds, (6)
Heterocyclic compounds, (7) non-heterocyclic organic sulfur compounds,
(8) quaternary ammonium salt compound, (9) aromatic nitrile compound, (10) phenol compound, (1
2. The microbicidal composition according to claim 1, which is at least one selected from the group consisting of 1) acetal compounds and (12) organic arsenic compounds. 3. The non-N-substituted benzoisothiazoline compound comprises (1) an ester compound, (2) an amide compound, (3) an alcohol compound, (4) a guanidine compound, and (5) a heterocyclic compound. The microbicidal composition according to claim 1, which is at least one selected from the group consisting of carbamate compounds and (6) heterocyclic compounds. 4. The composition according to claim 1, wherein the ratio of the N-substituted benzoisothiazoline compound is 1%.
The microbicide composition according to claim 1, wherein the amount is 0.01 to 2000 parts by weight based on parts by weight. 5. A method for controlling microorganisms, comprising adding the microbicidal composition according to claim 1 to a liquid to be treated. 6. The method according to claim 1, wherein the microbicidal composition is added to
The method according to claim 5, wherein the amount is from 3 to 30,000 ppm. 7. The method according to claim 5, wherein the N-substituted benzoisothiazoline compound is added in an amount of 1 to 20,000 ppm to the liquid to be treated. 8. The method according to claim 5, wherein the liquid to be treated is industrial water. 9. The liquid to be treated is: papermaking process water, industrial cooling water, circulating liquid of industrial manufacturing equipment, industrial washing water, industrial oil, latex, coating liquid, paste, paint, printing ink, The method according to claim 5, which is an adhesive or a sizing agent. 10. A method for adding the N-substituted benzoisothiazoline compound according to claim 1 to a microbicide to enhance the microbicidal action of said microbicide.