JP2000044406A - Microbicidal composition and method for retarding growth of microorganism - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a microbicidal composition exhibiting stronger microbicidal effect than that which each component individually has, exhibiting long-term antiseptic effect and being safe for workers by including a specific compound and an isothiazolone-based compound. SOLUTION: This microbicidal composition is prepared by including (A) 2,2-dibromo-2-nitroacetamide of the formula and (B) an isothiazolone-based compound selected from a group consisting of 5-chloro-2-methyl-4-isothiazolin-3- one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 1,2- benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 4,5- dichloro-2-n-octyl-4-isothiazolin-3-one, or its metal salt complex. The microbicidal composition can be thrown as one-component agent or two components A and B can simultaneously be thrown after stored separately, into objects to be sterilized and preserved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a non-medical microbicidal composition. Specifically, papermaking process water system of paper mill,
Bacteria that proliferate in products such as cooling water systems, cooling water systems, circulating water systems in various factories, metalworking oils, paper coating fluids, resin emulsions, fiber oils, water-based paints, glues, leather, etc. The present invention relates to a microbicidal composition used for sterilizing yeasts, filamentous fungi, and algae and for suppressing growth, and a method for suppressing the growth of microorganisms.

[0002]

2. Description of the Related Art Papermaking process water systems for paper mills, cooling water systems for cooling and heating equipment, circulating water systems for various factories, metal working oils, paper coating fluids, resin emulsions, fiber oils, water-based paints, pastes,
In products such as leather and the water system of the manufacturing process,
Various microorganisms, that is, bacteria, yeasts, filamentous fungi, and algae are multiplied by using the organic matter and a trace amount of inorganic substances contained in the water or the product as a nutrient source, and the quality and productivity of the product are significantly reduced.

[0003] For example, in the papermaking process water of paper and pulp mills,
At the place where the flow velocity slows down, a complex aggregate, in which pulp microfibers, resins such as sizing agents, paper strength enhancers, inorganic pigments, bacterial cells, etc. are incorporated into viscous substances secreted by these microorganisms, that is, a slime layer is formed You. The slime is exfoliated, mixed into the pulp slurry and made into paper, causing various problems. For example, the quality is degraded by causing spots on the product. On the other hand, the balance of the paper strength is lost, which may cause the paper to break. Especially in modern high speed papermaking machines, it leads to a large drop in productivity and enormous economic losses.

[0004] In the cooling water of cooling and heating equipment and the circulating water system of various factories, the generation of microorganisms is the main cause, which causes problems such as a decrease in heat exchange efficiency due to blockage of pipes and corrosion of pipes. In addition, products such as metalworking oils, paper coating liquids, latex, fiber oils, water-based paints, sizing agents, leather,
Also in these manufacturing processes, contamination and decay by microorganisms occur, and the quality of the product is deteriorated due to the contamination of the product, and the working environment is deteriorated due to unpleasant odor.

Conventionally, various microorganism control agents have been proposed to control the growth of such microorganisms. For example, isothiazolone compounds (JP-B-46-21240, JP-B-54-240)
23968), bromonitro alcohol-based compounds (JP-B-40-8917, JP-B-49-31095),
Organic bromine-based compounds (JP-B-42-10386, JP-B-46-12938, JP-B-49-4044, JP-B-52-12247) and organic sulfur-based compounds (JP-B-42-12247)
-16172, JP-B-52-14294, U.S. Pat. No. 3,306,810), isophthalonitrile-based compounds (JP-B-41-11358), aldehydes (JP-A-63-313705, JP-A-6-23368). And quaternary ammonium salts (JP-B-47-29363).

Recently, many microbicidal agents have been proposed which are imparted with additive to synergistic germicidal and preservative properties by mixing or simultaneously using these microbial control agents with other types of microbial control agents. ing.

In particular, 2,2-dibromo-3-nitrilopropionamide, which exhibits excellent rapid bactericidal activity against bacteria, is used not only as a single agent but also as a mixture mixed with various microbial control agents. (Tokoku 56-471
No. 63, Tokuhei 6-682). However, since this active ingredient has a very weak bactericidal effect against yeasts and filamentous fungi, for example, in combination with other active ingredients as described above, the strongest bactericidal effect most required at the site of use,
Moreover, it was not possible to satisfy a wide range of sterilization spectrum at the same time. In addition, since it has a cyano group in its structure, hydrogen cyanide generated in the course of decomposition is not a safe active ingredient, albeit in a small amount.

The first component of the present invention, 2,2-dibromo-2-nitroacetamide, which has a structure similar to that of 2,2-dibromo-3-nitrilopropionamide widely used in general, It is already known that it has antibacterial activity (JP-A-63-41402).
However, this 2,2-dibromo-2-nitroacetamide is used as a first component, and as a second component, a specific isothiazolone compound, nitro alcohol compound, organic bromine compound, organic sulfur compound, isophthalonitrile compound, No biological effects are known at all with aldehydes, quaternary ammonium salts, or co-additions.

[0009]

The present invention is directed to a wide variety of microorganisms such as bacteria, yeasts, filamentous fungi, and algae.
The present invention provides a non-medical microbicidal composition and a method for suppressing the growth of microorganisms, which exhibits a strong bactericidal effect and a long-term antiseptic effect that cannot be achieved by each active ingredient alone, and also considers safety for workers. The purpose is to do.

[0010]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies in view of the above-mentioned problems, and as a result, it has been found that 2,2-dibromo-2-nitroacetamide is a first component and a known antiseptic and preservative component as a second component. Specific isothiazolone compounds, nitro alcohol compounds, organic bromine compounds, organic sulfur compounds, isophthalonitrile compounds, aldehydes,
The present inventors have found that a microbicidal composition containing a quaternary ammonium salt and a method of simultaneously adding each active ingredient achieve the above object, and have accomplished the present invention based on this finding.

That is, the present invention provides:

Embedded image Wherein the second component is one or more selected from isothiazolone-based compounds or metal salt complexes of the following (1) to (6): A microbicidal composition containing. (1) 5-chloro-2-methyl-4-isothiazoline-
3-one (2) 2-methyl-4-isothiazolin-3-one (3) 2-n-octyl-4-isothiazolin-3-one (4) 1,2-benzisothiazolin-3-one (5) 2 -Methyl-4,5-trimethylene-4-isothiazolin-3-one (6) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one

(B) the first component represented by the formula (I):
A microbicidal composition which is 2-dibromo-2-nitroacetamide and wherein the second component contains one or more selected from nitro alcohol compounds shown in the following (7) to (13). (7) 2-bromo-2-nitropropane-1,3-diol (8) 2-bromo-2-nitrobutane-1,3-diol (9) 3-bromo-3-nitropentane-2,4-diol (10) 2,2-dibromo-2-nitro-1-ethanol (11) 3,3-dibromo-3-nitro-1-propanol (12) 1,1-dibromo-1-nitro-2-propanol (13 ) 5-Bromo-5-nitro-1,3-dioxane

(C) the first component represented by the formula (I) 2,
A microbicidal composition which is 2-dibromo-2-nitroacetamide, wherein the second component contains one or more selected from organic bromine compounds shown in the following (14) to (20). (14) 2,2-dibromo-3-nitrilopropionamide (15) 1,4-bis (bromoacetoxy) -2-butene (16) 1,2-bis (bromoacetoxy) ethane (17) 1,2- Bis (bromoacetoxy) propane (18) 2-bromo-2-nitro-1,3-diformyloxypropane (19) 2-bromo-2-nitro-1,3-diacetoxypropane (20) 2-bromo- 2-nitro-1,3-bisbromoacetoxypropane

(D) the first component represented by the formula (I) 2,
A microbicidal composition, which is 2-dibromo-2-nitroacetamide, wherein the second component contains one or more selected from the organic sulfur compounds shown in the following (21) to (23). (21) methylenebisthiocyanate (22) 4,5-dichloro-1,2-dithiol-3-one (23) 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide

(E) the first component represented by the formula (I) 2,
A microbicidal composition which is 2-dibromo-2-nitroacetamide, wherein the second component contains one or more selected from isophthalonitrile-based compounds shown in the following (24) to (26). (24) 5-chloro-2,4,6-trifluoroisophthalonitrile (25) 2,4,5,6-tetrafluoroisophthalonitrile (26) 2,4,5,6-tetrachloroisophthalonitrile

(F) the first component represented by the formula (I) 2,
A microbicidal composition which is 2-dibromo-2-nitroacetamide, wherein the second component contains one or more aldehydes selected from the following aldehydes (27) to (29). (27) orthophthalaldehyde (28) 1,5-pentanedial (29) formaldehyde

(G) wherein the first component is represented by the formula (I):
A microbicidal composition which is 2-dibromo-2-nitroacetamide, wherein the second component contains one or more quaternary ammonium salts shown in the following (30) to (32). (30) N, N-di-n-decyl-N, N-dimethylammonium chloride (31) N-alkyl-N, N-dimethyl-N-benzylammonium chloride <A mixture in which the alkyl chain has 12 to 18 carbon atoms> (32) N, N-di-n-decyl-N-methyl-N-hydroxyethylammonium propionate

(H) In a water system to be controlled by microorganisms,
It is intended to provide a method for simultaneously and / or separately adding the first component and the second component described in (a) to (g) to suppress sterilization and slime formation.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The microbicidal composition of the present invention comprises, as a first component, a 2,2-dibromo-formula represented by the above formula (I).
2-nitroacetamide, an isothiazolone-based compound as a second component, specifically 5-chloro-2-methyl-4-
Isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazoline-3-one
One selected from on, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one or a metal salt complex thereof Alternatively, two or more kinds can be contained. Particularly, as the isothiazolone-based compound as the second component, 5-chloro-2-
Methyl-4-isothiazolin-3-one and 2-methyl-
Mixtures with 4-isothiazolin-3-one, or metal salt complexes thereof, are preferred. These are usually available in mixtures.

The mixing ratio of 2,2-dibromo-2-nitroacetamide as the first component and the isothiazolone-based compound as the second component is as follows.
0.01 to 1 part by weight of 2-nitroacetamide
The amount is preferably 00 parts by weight, more preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight.

As the second component, a nitro alcohol compound, specifically, 2-bromo-2-nitropropane-
1,3-diol, 2-bromo-2-nitrobutane-
1,3-diol, 3-bromo-3-nitropentane-
2,4-diol, 2,2-dibromo-2-nitro-1
One selected from -ethanol, 3,3-dibromo-3-nitro-1-propanol, 1,1-dibromo-1-nitro-2-propanol, 5-bromo-5-nitro-1,3-dioxane or Two or more types can be contained. In particular, as the nitro alcohol compound as the second component, 2-bromo-2-nitropropane-1,3-diol and 2,2-dibromo-2-nitro-1-ethanol are preferred from the viewpoint of efficacy and cost.

The mixing ratio of 2,2-dibromo-2-nitroacetamide as the first component and the nitro alcohol compound as the second component is 1% by weight of 2,2-dibromo-2-nitroacetamide as the first component. 0.01 to part
It is preferably 50 parts by weight, more preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight.

The second component is an organic bromine compound,
Specifically, 2,2-dibromo-3-nitrilopropionamide, 1,4-bis (bromoacetoxy) -2-butene, 1,2-bis (bromoacetoxy) ethane, 1,2
-Bis (bromoacetoxy) propane, 2-bromo-2
-Nitro-1,3-diformyloxypropane, 2-bromo-2-nitro-1,3-diacetoxypropane, 2
One or two or more selected from -bromo-2-nitro-1,3-bisbromoacetoxypropane can be contained. Particularly, as the organic bromine-based compound as the second component, 1,4-bis (bromoacetoxy) -2-butene and 1,2-bis (bromoacetoxy) are preferred from the viewpoint of efficacy and cost.
Ethane is preferred.

The mixing ratio of 2,2-dibromo-2-nitroacetamide of the first component and the above-mentioned organic bromine compound as the second component is 1% by weight of 2,2-dibromo-2-nitroacetamide of the first component. Parts by weight is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight,
Particularly preferred is 0.5 to 10 parts by weight.

As the second component, an organic sulfur compound,
Specifically, methylene bisthiocyanate, 4,5-dichloro-1,2-dithiol-3-one, 3,3,4,4
One or more selected from tetrachlorotetrahydrothiophene-1,1-dioxide. The mixing ratio of 2,2-dibromo-2-nitroacetamide as the first component and the organic sulfur-based compound as the second component is 1 part by weight of 2,2-dibromo-2-nitroacetamide as the first component. It is preferably 0.01 to 100 parts by weight, more preferably 0.05 to 50 parts by weight, and particularly preferably 0.1 to 10 parts by weight.

The second component is an isophthalonitrile compound, specifically, 5-chloro-2,4,6-trifluoroisophthalonitrile, 2,4,5,6-tetrafluoroisophthalonitrile, , 4,5,6-tetrachloroisophthalonitrile. The mixing ratio of 2,2-dibromo-2-nitroacetamide of the first component and the isophthalonitrile compound as the second component is 1 part by weight of 2,2-dibromo-2-nitroacetamide of the first component. 0.01 to 50 parts by weight, preferably 0.05 to 2 parts by weight
0 parts by weight is more preferable, and 0.1 to 5 parts by weight is particularly preferable.

The second component may contain an aldehyde, specifically one or more selected from orthophthalaldehyde, 1,5-pentanedial, and formaldehyde. The mixing ratio of 2,2-dibromo-2-nitroacetamide of the first component and the aldehyde as the second component is 0.01 to 1 part by weight of 2,2-dibromo-2-nitroacetamide of the first component. ~
It is preferably 50 parts by weight, more preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight.

As the second component, a quaternary ammonium salt, specifically, N, N-di-n-decyl-N, N-dimethylammonium chloride, N-alkyl-N, N-dimethyl-N-benzylammonium It may contain one or more selected from chloride (a mixture in which the alkyl chain has 12 to 18 carbon atoms) and N, N-di-n-decyl-N-methyl-N-hydroxyethylammonium propionate. it can. 2,2-dibromo-2 of the first component
The mixing ratio of nitroacetamide and the quaternary ammonium salt as the second component is 0.0 to 1 part by weight of 2,2-dibromo-2-nitroacetamide of the first component.
The amount is preferably 1 to 50 parts by weight, more preferably 0.05 to 20 parts by weight, and particularly preferably 0.1 to 10 parts by weight.

The second component, an isothiazolone compound, a nitro alcohol compound, an organic bromine compound, an organic sulfur compound, an isophthalonitrile compound, an aldehyde,
Two or more bactericidal preservatives of the quaternary ammonium salt may be selected and used in combination with the first component, 2,2-dibromo-2-nitroacetamide, for sterilization and preservation.

The microbicidal composition according to the present invention is capable of dissolving or suspending the first and second active ingredients in water or an organic solvent. If necessary, a surfactant, a rust inhibitor, By blending a stabilizer, an auxiliary, and other additives, a liquid preparation such as a water-soluble liquid preparation, an emulsifier, and a microemulsion preparation can be obtained.

Suitable solvents other than water include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and having an average molecular weight of 200-4.
Polyethylene glycol of about 00, average molecular weight of 30
A glycol solvent such as polypropylene glycol of about 0 to 500, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,
Glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether are priced, the solubility of the active ingredient, and It is suitable in terms of stability of the active ingredient and the like. These solvents may be used alone, or two or more kinds may be mixed and used as a mixed solvent to which water is further added.

Further, in order to prevent freezing in a severe winter or to further improve the stability of the active ingredient, propylene carbonate is used.
It can be used by dissolving it in an aprotic solvent such as N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, γ-butyrolactone, and dimethyl maleate. Also in this case, the aprotic solvent may be used alone, or two or more kinds may be mixed. Further, it can be used as a mixed solvent with a glycol solvent, a glycol ether solvent, and water.

Although the microbicidal composition of the present invention can be easily added as a one-part solution to the object of sterilization and preservation, it is preferable to separate the first component and the second component from the viewpoint of long-term storage stability. In such a case, each component can be separately prepared and can be simultaneously added to the object of sterilization and preservation. Even in such a charging method, as long as the charging ratio and the charging amount of the first component and the second component are the same as those of the one-part preparation, the germicidal and preservative effect is not different from that of the one-part preparation.

The proper use amount of the microbicidal composition of the present invention is as follows: the water system to be sterilized and preserved, the susceptibility of the object to spoilage, that is, the amount of organic and inorganic substances as a nutrient source of microorganisms, open or closed system, temperature. Although it differs depending on the species of the microorganisms to be propagated and cannot be mentioned unconditionally, it is generally 10 to 500 pp with respect to the total weight of the water used or the weight of the object to be sterilized and preserved.
It is preferred to use at a concentration of m. It is more preferable to use in the range of 50 to 200 ppm in consideration of economy and bactericidal and preservative effect.

[0035]

The microbicidal composition and the method for inhibiting the growth of microorganisms according to the present invention provide a strong synergistic fungicidal and antiseptic effect by using 2,2-dibromo-2-nitroacetamide in combination with a specific antiseptic and preservative component. Alternatively, a wide range of sterilization spectra can be obtained. It is particularly suitable for sterilizing white water in paper mills and for sterilizing and preserving starch slurries, coating solutions and resin emulsions.

[0036]

EXAMPLES The present invention will be described in more detail with reference to examples. The following formulation (% by weight) gave a microbicidal composition according to the invention. In addition, 2,2-dibromo-2-nitroacetamide (abbreviation: DBNA), which is the first component of the microbicidal composition of the present invention, has a purity of 99.0% synthesized by KI Chemical Co., Ltd. The two effective components for controlling microorganisms were commercially available products easily available or those synthesized by K-I Kasei Co., Ltd., all of which were described by trade names or abbreviations.

Example 1 DBNA 12.5% Caisson WT ^{* 1} 18.5% Diethylene glycol 69.0% Total 100.0% Example 2 DBNA 12.5% Zonene F ^{* 2} 18.5% Ethylene glycol 69.0 % Total 100.0% Example 3 DBNA 10.0% SKANE M-8 ^{* 3} 4.5% Propylene glycol 85.5% Total 100.0% Example 4 DBNA 7.5% XBINX ^{* 4} 13.5% Ethylene glycol 34.0% N, N-dimethylacetamide 45.0% Total 100.0%

Example 5 DBNA 10.0% BNPK ^{* 5} 16.0% diethylene glycol 74.0% total 100.0% Example 6 DBNA 5.0% BNBD ^{* 6} 25.0% diethylene glycol 70.0% total 100 0.0% Example 7 DBNA 15.0% BNPD ^{* 7} 7.0% Diethylene glycol 78.0% Total 100.0% Example 8 DBNA 8.0% BNDO ^{* 8} 12.5% Diethylene glycol 79.5% Total 100 0.0% Example 9 DBNA 10.0% Dibunilol A-75 ^{* 9} 21.5% Polyethylene glycol 200 25.0% Diethylene glycol 43.5% Total 100.0% Example 10 DBNA 10.0% DBNP ^{* 10} 16 .0% polyethylene glycol 200 25.0% diethylene glycol 49.0% total 100.0 Example ^{11 DBNA 12.5% DBNP-K *} 11 8.5% polyethylene glycol 200 30.0% Diethylene glycol 49.0% Total 100.0%

Example 12 DBNA 12.5% B-14 ^{* 12} 23.5% Propylene carbonate 25.0% γ-butyrolactone 39.0% Total 100.0% Example 13 DBNA 12.5% BBAE ^{* 13} 23 2.5% propylene carbonate 25.0% γ-butyrolactone 39.0% total 100.0% Example 14 DBNA 12.5% BNDAP ^{* 14} 21.0% propylene carbonate 20.5% γ-butyrolactone 46.0% total 100.0% Example 15 DBNA 12.5% BNBAP ^{* 15} 21.0% Propylene carbonate 20.5% γ-butyrolactone 46.0% Total 100.0%

Example 16 DBNA 7.0% MBT ^{* 16} 15.0% Ethylene glycol monoethyl ether 78.0% Total 100.0% Example 17 DBNA 5.5% Microvan 86 ^{* 17} 5.0% ethylene Glycol monoethyl ether 89.5% in total 100.0% Example 18 DBNA 5.5% Slavan ^{* 18} 35.0% Diethylene glycol monomethyl ether 59.5% in total 100.0%

Example 19 DBNA 8.0% SDB-028 ^{* 19} 4.5% Propylene carbonate 25.0% γ-butyrolactone 62.5% Total 100.0% Example 20 DBNA 10.0% SDB-018 ^{* 20} 7.5% Propylene carbonate 25.0% γ-butyrolactone 57.5% Total 100.0%

Example 21 DBNA 12.5% OP-100S ^{* 21} 10.0% Dipropylene glycol monomethyl ether 77.5% Total 100.0% Example 22 DBNA 8.0% Pyrrole 850 ^{* 22} 60.0% Ethylene glycol 32.0% Total 100.0%

Example 23 DBNA 12.5% Bardac 2280 ^{* 23} 5.0% Ethylene glycol 35.0% Water 47.5% Total 100.0% Example 24 DBNA 12.5% Cation G-50 ^{* 24} 8.0% Ethylene glycol 35.0% Water 44.5% Total 100.0%

Comparative Example 1 Caisson WT ^{* 1} 28.0% Water 72.0% Total 100.0% Comparative Example 2 SKANE M-8 ^{* 3} 6.5% Propylene Glycol 93.5% Total 100.0% Example 3 XBINX ^{* 4} 20.0% Ethylene glycol 40.0% N, N-dimethylacetamide 40.0% Total 100.0%

Comparative Example 4 BNPK ^{* 5} 22.5% diethylene glycol 77.5% total 100.0% Comparative Example 5 BNBD ^{* 6} 32.5% diethylene glycol 67.5% total 100.0% Comparative Example 6 BNPD ^{* 7} 12 .5% diethylene glycol 87.5% total 100.0% Comparative example 7 BNDO ^* 8 18.0% diethylene glycol 82.0% total 100.0% Comparative example 8 Jibuniroru A-75 ^* 9 32.0% polyethylene glycol 200 28 0.0% diethylene glycol 200 40.0% total 100.0% Comparative Example 9 DBNP ^{* 10} 17.5% Polyethylene glycol 200 37.5% diethylene glycol 200 45.0% total 100.0% Comparative Example 10 DBNP-K ^{* 11} 14.5% polyethylene glycol 200 37.5% diethylene glycol 2 0 48.0% Total 100.0%

Comparative Example 11 B-14 ^{* 12} 35.0% Propylene Carbonate 25.0% γ-butyrolactone 40.0% Total 100.0% Comparative Example 12 BBAE ^{* 13} 35.0% Propylene Carbonate 25.0% γ -Butyrolactone 40.0% total 100.0% Comparative Example 13 BNDAP ^{* 14} 30.0% Propylene carbonate 25.0% γ-butyrolactone 45.0% total 100.0% Comparative Example 14 BNBAP ^{* 15} 30.0% Carbonic acid Propylene 25.0% γ-butyrolactone 45.0% Total 100.0%

Comparative Example 15 MBT ^{* 16} 20.0% Ethylene Glycol Monoethyl Ether 80.0% Total 100.0% Comparative Example 16 Microvan 86 ^{* 17} 7.5% Ethylene Glycol Monoethyl Ether 92.5% Total 100 0.0% Comparative Example 17 Suracarb ^{* 18} 50.0% Ethylene glycol monomethyl ether 50.0% Total 100.0%

Comparative Example 18 SDB-028 ^{* 19} 7.5% Propylene Carbonate 92.5% Total 100.0% Comparative Example 19 SDB-018 ^{* 20} 10.0% Propylene Carbonate 90.0% Total 100.0%

Comparative Example 20 OP-100S ^{* 21} 17.5% Dipropylene glycol monomethyl ether 82.5% Total 100.0% Comparative Example 21 Pyrrole 850 ^{* 22} 75.0% Water 25.0% Total 100.0 %

Comparative Example 22 Bardak 2280 ^{* 23} 10.0% Water 90.0% Total 100.0% Comparative Example 23 Cation G-50 ^{* 24} 12.5% Water 87.5% Total 100.0%

Comparative Example 24 DBNA 20.0% Ethylene Glycol 80.0% Total 100.0% Comparative Example 25 DBNA 35.0% Propylene Carbonate 65.0% Total 100.0%

[0052]

Test Example 1 (Preservative test) 10% starch slurry (pH
7.5) was prepared and a single colony was separated from the spoiled starch slurry, and the obtained three strains ( Pseudomonas genus bacteria, Aeromonas genus bacteria, Alcaligen ) were obtained.
A bacterium belonging to the genus es ) was inoculated in a broth medium overnight at 0.5% of a culture solution pre-cultured.

This starch slurry was placed in a tall beaker for 50 minutes.
g of each composition was added, and a predetermined amount of each composition shown in Examples and Comparative Examples was added. Capped with aluminum foil and allowed to stand in a thermo-hygrostat at 30 to 35 ° C. After 7 days and 21 days, the number of viable bacteria in each starch slurry was measured and the odor was confirmed. Examined. In order to further clarify the persistence of the preservative effect, the bacteria were re-inoculated after 7 days and 21 days after measuring the number of bacteria and confirming the odor.

Tables 1 to 5 show the test results. The unit of the viable cell count in the table is CFU / ml, and the odor intensity is expressed as-: odorless to slight off-flavor, ±: weak rot smell, +: strong rot smell. As for the active ingredient in each sample, 2,2-dibromo-2-nitroacetamide as the first component was DBNA.
And the second component was also represented by a trade name or abbreviation. Controls to which no drug was added were shown as blanks.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

[Table 5]

[0060]

[Test Example 2] (Slime suppression test) A plastic water channel with a length of 100 cm, a width of 5 cm, and a height of 4 cm, which was fixed with an inclination of about 10 ° (width of 2 cm, height of 4 to block running water at 4 places)
cm water resistance plate), a water receiver, a water circulation pump, a precision metering pump for adding a chemical solution equipped with a timer, and a five-line water circulation device composed of PVC piping at a temperature of 25 to 2
It was installed in a laboratory room adjusted to 7 ° C. and a humidity of 70 to 80%. According to this device, the water that has flowed down the water passage temporarily accumulates in the water receiver, and then returns to the upstream of the water passage again by the circulation pump. A temperature controller and a stirrer were installed in the water receiver to control the temperature of the circulating water. The circulating water was continuously overflowed from the water receiver, and the same amount of new water including the evaporation was supplied from a makeup water tank (with a stirrer) by a pump. One of the five water circulation devices was used as a blank section without adding a chemical.

The circulating water used in this test was white water (pulp 0.01%, calcium carbonate 0.0
5%, polyacrylamide 0.01%, meat extract peptone medium 0.05%, pH 5-6). This white water 2
After adding 0 liter to each water reservoir and adjusting the temperature to 30 to 35 ° C., two bacterial strains (unidentified), two yeast strains (unidentified), and one filamentous fungus strain (unidentified) isolated from paper mill white water. The test was started by inoculating 100 ml of the preculture solution of (1) into each water reservoir. Each water circulation pump is about 20 liters /
The operation was performed at the speed of time, and the amount of overflow, that is, the supply of fresh white water, was about 5 liters / hour. For the addition of the chemical solution, a precision metering pump was used to charge 1.0 ml (50 ppm as the drug concentration) into each water reservoir every 8 hours.

As described above, the white water was circulated, and seven days after the start of the test, all the slime layer attached to the water passage was scraped off. Spread this on a 20cm mesh sieve (12 mesh)
The sample was allowed to stand for 1 hour in a thermo-hygrostat at a temperature of 20 ° C. and a humidity of 80%, and the wet weight after excess water was removed was measured to determine the amount of adhered slime. Tables 6 to 14 show the slime suppressing effects of the examples according to the present invention.

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

[0067]

[Table 10]

[0068]

[Table 11]

[0069]

[Table 12]

[0070]

[Table 13]

[0071]

[Table 14]

[0072]

[Test Example 3] (Confirmation test of synergistic effect) Bacteria ( Enterobacter ) were added to a phosphate-citrate buffer at pH 6.5.
aerogenes ) or a filamentous fungus ( Geotric )
um candidum ) and 10 ⁴ to 10 ⁵ C
An FU / ml cell suspension was prepared. Predetermined amounts of this cell suspension and the first and second components of the microbicidal composition of the present invention were added to an L-shaped tube, and shaking culture was performed at 30 ° C. for 30 minutes or 2 hours.

After 30 minutes or 2 hours of contact with the drug, the viable cell count is measured by the agar plate pour method, and the minimum bactericidal concentration in the mixture of the first and second components, and each of the first and second components, The minimum bactericidal concentration alone was determined. The minimum bactericidal concentration under the test conditions is that the viable cell count is 10 ² C
The drug concentration was defined as FU / ml, and the determination was made.

The interaction between the first component and the second component is described in F.
C. Kull, P .; C. Eisman, H .; D. Syl
westrowicz and R.C. L. Mayer et al., Applied Microbiology (Applied M
microbiology), Volume 9, 538-541
Page, (1961), as determined by commonly used and accepted methods. According to this method,
The synergistic ratio between the first component and the second component is obtained by the following equation.

[0075]

(Equation 1)

Qa: Minimum bactericidal concentration of the first component alone. QA: Concentration of the first component in the mixture showing the minimum bactericidal concentration. Qb: minimum bactericidal concentration of the second component alone. QB: concentration of the second component in the mixture showing the minimum bactericidal concentration.

When the synergistic ratio is greater than 1, antagonism and 1
Indicates an additive effect, and a value less than 1 indicates a synergistic effect. The first component of the microbicidal composition of the present invention, namely 2,2
Table 15 shows the bactericidal effect by the interaction between -dibromo-2-nitroacetamide and each of the microbial control active ingredients of the second component.
To Table 34.

[0078]

[Table 15]

[0079]

[Table 16]

[0080]

[Table 17]

[0081]

[Table 18]

[0082]

[Table 19]

[0083]

[Table 20]

[0084]

[Table 21]

[0085]

[Table 22]

[0086]

[Table 23]

[0087]

[Table 24]

[0088]

[Table 25]

[0089]

[Table 26]

[0090]

[Table 27]

[0091]

[Table 28]

[0092]

[Table 29]

[0093]

[Table 30]

[0094]

[Table 31]

[0095]

[Table 32]

[0096]

[Table 33]

[0097]

[Table 34]

* 1 Active ingredient: 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one mixture manufactured by Rohm and Haas Company Content: 5-chloro- 2-Methyl-4-isothiazolin-3-one 11% 2-methyl-4-isothiazolin-3-one 3% Trade name: Caisson WT * 2 Ichikawa Gosei Chemical Co., Ltd. Active ingredient: 5-chloro-2-methyl- 4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one mixture content: 5-chloro-2-methyl-4-isothiazolin-3-one 11% 2-methyl-4-isothiazolin-3-one ON 1% Product name: Zonen F * 3 manufactured by Rohm and Haas Active ingredient: 2-n-octyl-4-isothiazolin-3-one Content: 45% Product name : SKANE M-8 * 4 manufactured by PMC Active ingredient: 1,2-benzisothiazolin-3-one Content: 75% Trade name: XBINX

* 5 manufactured by K-I Kasei Co., Ltd. Active ingredient: 2-bromo-2-nitropropane-1,3-diol Content:> 98.5% Trade name: BNPK * 6 manufactured by K-I Kasei Active ingredient: 2-bromo-2-nitrobutane-1,3-diol Content:> 99% Abbreviation: BNBD * 7 K-I Kasei Co., Ltd. Active ingredient: 3-bromo-3-nitropentane-2,4 -Diol content:> 99% Abbreviation: BNPD * 8 Active ingredient: 5-bromo-5-nitro-1,3-dioxane content:> 99% Abbreviation: BNDO * 9 -Active ingredient manufactured by I-Kasei Co., Ltd .: 2,2-dibromo-2-nitro-1-ethanol Content: 75% Trade name: dibunirole A-75 * 10 Active ingredient: 3,3 manufactured by K-I Kasei Corporation Dibromo-3-nitro-1-propanol content:> 99% Abbreviation: DBNP * 11 manufactured by K-I Kasei Co., Ltd. Active ingredient: 1,1-dibromo-1-nitro-2-propanol content:> 99% Abbreviation: DBNP-K

* 12 Active ingredient: Ichikawa Gosei Chemical Co., Ltd. Active ingredient: 1,4-bis (bromoacetoxy) -2-butene Content: 90% Trade name: B-14 * 13 Active ingredient: Ichikawa Gosei Chemical Co., Ltd .: 1 , 2-Bis (bromoacetoxy) ethane Content: 90% Trade name: BBAE * 14 manufactured by K-I Kasei Co., Ltd. Active ingredient: 2-bromo-2-nitro-1,3-diacetoxypropane Content:> 99 % Abbreviation: BNDAP * 15 Active ingredient: 2-bromo-2-nitro-1,3-bisbromoacetoxypropane Content:> 99% Abbreviation: BNBAP

* 16 manufactured by Rohm and Haas Co. Active ingredient: methylene bisthiocyanate Content:> 98% Trade name: MBT * 17 manufactured by Yoshitomi Pharmaceutical Co., Ltd. Active ingredient: 4,5-dichloro-1,2-dithiol- 3-one content: 20% Trade name: Microvan 86 * 18 manufactured by Takeda Pharmaceutical Co., Ltd. Active ingredient: 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide Content:> 95% Product Name: Slab

* 19 SDS Biotech Inc. Active ingredient: 5-chloro-2,4,6-trifluoroisophthalonitrile Content:> 98% Trade name: SDB-028 * 20 -DS Biotech Active ingredient: 2,4,5,6-tetrafluoroisophthalonitrile Content:> 98% Trade name: SDB-018

[0103]

* 23 manufactured by Lonza Active ingredient: N, N-di-n-decyl-N, N-dimethylammonium chloride Content: 80% Trade name: Verdac 2280 * 24 Active ingredient: N manufactured by Sanyo Chemical Industries, Ltd. - alkyl -N, N-dimethyl -N- benzyl ammonium Niu arm chloride (alkyl chain _{C 12 60%, C 14 35} %, mixture of C ₁₆ 5%) containing volume: 50% product name: cationic G-50

Claims (8)

[Claims] The first component has the formula: Wherein the second component is one or more selected from isothiazolone-based compounds or metal salt complexes of the following (1) to (6): A microbicidal composition containing. (1) 5-chloro-2-methyl-4-isothiazoline-
3-one (2) 2-methyl-4-isothiazolin-3-one (3) 2-n-octyl-4-isothiazolin-3-one (4) 1,2-benzisothiazolin-3-one (5) 2 -Methyl-4,5-trimethylene-4-isothiazolin-3-one (6) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one 2. The method according to claim 1, wherein the first component has the formula A microbialicidal composition comprising a 2,2-dibromo-2-nitroacetamide represented by the formula: wherein the second component contains one or more nitro alcohol compounds selected from the following (7) to (13): object. (7) 2-bromo-2-nitropropane-1,3-diol (8) 2-bromo-2-nitrobutane-1,3-diol (9) 3-bromo-3-nitropentane-2,4-diol (10) 2,2-dibromo-2-nitro-1-ethanol (11) 3,3-dibromo-3-nitro-1-propanol (12) 1,1-dibromo-1-nitro-2-propanol (13 ) 5-Bromo-5-nitro-1,3-dioxane 3. The method of claim 1, wherein the first component is of the formula A microbialicidal composition comprising a 2,2-dibromo-2-nitroacetamide represented by the formula: wherein the second component contains one or more selected from the organic bromine compounds shown in the following (14) to (20): object. (14) 2,2-dibromo-3-nitrilopropionamide (15) 1,4-bis (bromoacetoxy) -2-butene (16) 1,2-bis (bromoacetoxy) ethane (17) 1,2- Bis (bromoacetoxy) propane (18) 2-bromo-2-nitro-1,3-diformyloxypropane (19) 2-bromo-2-nitro-1,3-diacetoxypropane (20) 2-bromo- 2-nitro-1,3-bisbromoacetoxypropane 4. The method according to claim 1, wherein the first component is of the formula A microbialicidal composition comprising a 2,2-dibromo-2-nitroacetamide represented by the formula: wherein the second component contains one or more selected from organic sulfur compounds shown in the following (21) to (23): object. (21) methylenebisthiocyanate (22) 4,5-dichloro-1,2-dithiol-3-one (23) 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide 5. The method of claim 1, wherein the first component is of the formula Is a 2,2-dibromo-2-nitroacetamide represented by the formula: wherein the second component contains one or more selected from isophthalonitrile compounds shown in the following (24) to (26). Composition. (24) 5-chloro-2,4,6-trifluoroisophthalonitrile (25) 2,4,5,6-tetrafluoroisophthalonitrile (26) 2,4,5,6-tetrachloroisophthalonitrile 6. The method according to claim 1, wherein the first component is of the formula A microbicidal composition comprising 2,2-dibromo-2-nitroacetamide represented by the formula (1), wherein the second component contains one or more aldehydes selected from the following aldehydes (27) to (29). (27) orthophthalaldehyde (28) 1,5-pentanedial (29) formaldehyde 7. The method of claim 1, wherein the first component is of the formula Wherein the second component comprises one or more quaternary ammonium salts selected from the following (30) to (32): Composition. (30) N, N-di-n-decyl-N, N-dimethylammonium chloride (31) N-alkyl-N, N-dimethyl-N-benzylammonium chloride <A mixture in which the alkyl chain has 12 to 18 carbon atoms> (32) N, N-di-n-decyl-N-methyl-N-hydroxyethylammonium propionate 8. A method for suppressing the sterilization and slime formation by simultaneously and / or separately adding the first component and the second component according to claim 1 to an aqueous system to be controlled by microorganisms. .