JPH092907A - Harmful microbe exterminator - Google Patents

Abstract

PURPOSE: To obtain a highly stable exterminator presenting unique synergistic effect, capable of effectively disinfecting and controlling a wide range of harmful microbes and/or suppressing their breeding, by combining two or three kinds of each specific agent having antimicrobial power. CONSTITUTION: This harmful microbe exterminator is a combination of (A) a halogenoacetic ester as an industrial germicide, (B) 3,3,4,4- tetrachlorotetrahydrothiophene-1,1-dioxide, and, optionally, (C) a compound selected from isothiazolone-based compounds and organohalogen compounds of formula I (X<1> is a halogen; Y is nitro or cyano; R<1> and R<2> are each a halogen, nitro, alkyl, etc.). The weight ratio A/B is pref. (100:1) to (1:100); and it is recommended that the component C accounts for 1-100wt.% of the component A plus B. The component A is pref. a compound of formula II (X<2> and X<3> are each a halogen; L is an alkylene, etc.). This new exterminator is used in paper and pulp irrigation systems and various industrial areas.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a novel harmful microbial eradication agent, and more particularly, has a broad antibacterial spectrum.
In addition to exhibiting excellent antibacterial and antifungal effects, it also has an excellent effect of suppressing the growth of various microorganisms and has high stability, and is a harmful substance suitable for use in various industrial fields including water systems in the pulp and paper industry. It relates to a microbial eradication agent.

[0002]

2. Description of the Related Art Conventionally, various water systems in the pulp and paper industry, such as white water in the papermaking process and circulating cooling water in various industries, as well as water-based paints and papers prepared using industrial water. In the fields of coating liquids for coatings, latexes, polymer emulsions, printing pastes, adhesives, metalworking oils such as cutting oils, leather, and wood, harmful microorganisms easily proliferate, which reduces productivity and quality. Is the cause. Especially in the water system in the pulp and paper industry,
Slime is generated by the proliferation of bacteria, filamentous fungi, and yeasts, and the flow path of pulp slurry, especially the rough wall surface where the slurry contacts, chests, flow boxes, transport pipes, and other pipes Adhesion formation of slime becomes visible at the place where it occurs.

The slime is often desorbed, which causes paper scraps and contamination of pulp and paper products, and causes various obstacles due to the growth of microorganisms.

The occurrence of such a failure becomes a serious drawback particularly when using a high speed machine, resulting in a significant decrease in productivity and an economic loss.

Further, the proliferation of microorganisms in a circulating water system for cooling such as a metalworking oil agent causes a phenomenon which is unfavorable to public health, such as impairing the cooling performance and emulsifying property and generating a bad odor and deteriorating the working environment. cause.

[0006] In addition, obstacles due to the proliferation of harmful microorganisms are also found in industrial products such as water-based paints, paper coating liquids, polymer latexes, papermaking pulps, pastes, leathers, and metalworking oils.

By the way, organometallic compounds, organosulfur compounds, quaternary ammonium salt compounds and the like have hitherto been used as agents for suppressing or controlling the generation of harmful microorganisms in the water system and the industrial products. However, in addition to these compounds being toxic to the human body,
This may cause an offensive odor or an offensive odor, and further cause an undesirable phenomenon such as foaming. Moreover, when these control agent-containing water systems are thrown into general rivers or the sea, they adversely affect fish and shellfish and cause environmental problems.

In order to avoid such drawbacks, a non-agricultural antifungal preservative containing halogenoacetic acid ester as an active ingredient (Japanese Patent Publication No. 52-12247), 3, 3, 3.
4,4-tetrachlorotetrahydrothiophene-1,1
A disinfectant comprising -dioxide (US Pat. No. 295788)
No. 7, etc.) have been proposed, but since these have limited effective microorganisms and a broad spectrum of antibacterial spectrum cannot be obtained, their application range is inevitable and they are not always satisfactory as harmful microorganism eradication agents. Not profitable.

[0009]

Under the circumstances described above, the present invention has a broad antibacterial spectrum and exhibits excellent antibacterial and antifungal effects against many microorganisms and breeds various microorganisms. The purpose of the present invention is to provide a harmful microorganism eradicating agent that can effectively suppress the above-mentioned problems and is highly stable.

[0010]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted various studies to develop a harmful microorganism eradicating agent having a wide range of application, and as a result, the halogenoacetic acid ester which has been used as a conventional industrial bactericide is obtained. It was found that the objective can be achieved by combining 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, or further an isothiazolone compound or a specific halogen-containing organic compound, and based on this finding, The present invention has been completed based on the above.

That is, the present invention relates to (A) a halogenoacetic acid ester, (B) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and optionally (C) an isothiazolone compound and (B) General formula

Embedded image (Wherein X ¹ is a halogen atom, Y is a nitro group or a cyano group, R ¹ and R ² are a halogen atom, a nitro group, a cyano group, a hydroxyl group, an aminocarbonyl group or a substituted or unsubstituted alkyl group, respectively. And they may be the same or different from each other), and provides a harmful microorganism eradicating agent containing at least one selected from the compounds represented by .

As the halogenoacetic acid ester of the component (A) in the harmful microbial eradication agent of the present invention, a compound of the general formula

Embedded image (Wherein X ² and X ³ are each a halogen atom, and they may be the same or different from each other, and L is an alkylene group or an alkenylene group). Things are used.

Examples of the halogen atom for X ² and X ³ in the general formula (II) include Cl, Br and the like. X ² and X ³ may be the same or different. The alkylene group in L is, for example, an ethylene group, a propylene group, a trimethylene group, a butylene group, a pentamethylene group or a hexamethylene group, and the alkenylene group is, for example, a propenylene group, a butenylene group or a hexenylene group. Can be mentioned.
As the component (A), X ² and X ³ are both Br,
Bisbromoacetoxyethane in which L is —CH ² —CH ² — is preferable because it has excellent bactericidal activity against bacteria and mold. In addition, as the component (A), for example, 1,2-
Examples thereof include bisbromoacetoxybutene, 1,2-bisbromoacetoxypropane and 1,2-bischloroacetoxyethane. These may be used alone or 2
A combination of more than one species may be used.

In the harmful microorganism eradication agent of the present invention, (B)
The 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide used as a component has the formula

Embedded image It is represented by

In the harmful microbial eradication agent of the present invention, the mixing ratio of the component (A) and the component (B) is preferably 1: 100 to 100: 1 by weight. When the mixing ratio of both components is within this range, an excellent synergistic effect is exhibited against both bacteria and mold. When the ratio of the component (A) is less than the above range [when the ratio of the component (B) is more than the above range], the efficacy against bacteria is not sufficiently exerted, and when the ratio of the component (A) is more than the above range [ When the ratio of the component (B) is less than the above range], the efficacy against mold is reduced. From the viewpoint of exerting an excellent synergistic effect and exhibiting high efficacy against both bacteria and mold, the particularly preferable mixing ratio of the component (A) and the component (B) is in the range of 1:50 to 50: 1. .

In the harmful microbial eradication agent of the present invention, if desired, together with the above-mentioned components (A) and (B), (C)
As components, (a) isothiazolone compounds and (b) general formula

Embedded image A compound represented by the formula (X ¹ , Y, R ¹ and R ² have the same meanings as described above) can be contained.

The isothiazolone compound of the above-mentioned component (a) is usually represented by the general formula

[Chemical 6] (R ³ in the formula is a hydrogen atom, an alkyl group, an alkenyl group,
The alkynyl group or aralkyl group, R ⁴ and R ⁵ are each a hydrogen atom or a halogen atom, which may be the same or different from each other, or are bonded to each other to form a benzene condensed ring. Which may have been formed) is used.

In the general formula (III), among the groups represented by R ³ , the alkyl group is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-group.
Butyl group, isobutyl group, sec-butyl group, tert
-Butyl group, octyl group and the like, alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group and the like, alkynyl groups such as ethynyl (acetylenyl)
Group, propynyl group, propargyl group and the like, and aralkyl group includes, for example, benzyl group, phenethyl group and the like. Further, among the groups represented by R ⁴ and R ⁵ , examples of the halogen atom include F, Cl, Br and the like.

Examples of such compounds include 5-chloro-2-methyl-4-isothiazolin-3-one and 2
-Methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 4,5-dichloro-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one Especially, 5-
Chloro-2-methyl-4-isothiazolin-3-one and is preferred because of their high bactericidal activity. These isothiazolone compounds may be used alone or in combination of two or more. When two or more kinds are used in combination, a mixture with 2-methyl-4-isothiazolin-3-one is preferable because it has excellent bactericidal properties and fungicidal properties.

Further, the isothiazolone compound used in the harmful microbial eradication agent of the present invention is complexed with a metal salt such as copper nitrate, magnesium nitrate, calcium chloride, zinc chloride or potassium bromate in order to improve stability. Good. For example 5-chloro-2-methyl-3-
Isothiazolone magnesium nitrate, 2-methyl-3-isothiazolone magnesium nitrate, 2-
Examples include octyl-4-chloro-3-isothiazolone calcium chloride, and these may be used alone or in combination of two or more kinds. 5-
Since the combination of chloro-2-methyl-3-isothiazolone magnesium nitrate, 2-methyl-3-isothiazolone magnesium nitrate has a good stability on storage and an excellent bactericidal effect against bacteria in the pulp and paper industry papermaking system. preferable.

On the other hand, in the compound represented by the general formula (I) as the component (b), X ¹ is a halogen atom such as Cl and Br, and Y is a nitro group or a cyano group. Also R ¹
And R ² are each a halogen atom such as Cl and Br, a nitro group, a cyano group, a hydroxyl group, an aminocarbonyl group or a substituted or unsubstituted alkyl group. Here, examples of the substituted alkyl group include a hydroxyalkyl group, an acyloxyalkyl group, a bromoalkyl group, and a cyanoalkyl group. R ¹ and R ² may be the same or different.

Examples of the compound represented by the general formula (I) include 2,2-dibromo-2-nitroethanol, 1,2-dibromo-1-nitropropanol,
2,2-dibromo-3-nitrilopropionamide, 2
-Bromo-2-nitropropane-1,3-diol,
1,1-dibromo-1-nitro-2-acetoxyethane, 1,1-dibromo-1-nitro-2-acetoxypropane, 2-bromo-2-nitro-1,3-diacetoxypropane, 1,2- Dibromo-2,4-dicyanobutane, 2-bromo-2-nitro-1,3-diacetoxypropane and the like can be mentioned. These (b) component compounds may be used alone or in combination of two or more.

In the harmful microorganism eradication agent of the present invention,
As the component (C), one type of the isothiazolone compound of the above-mentioned component (A) may be used, or two or more types thereof may be used in combination, and the compound represented by the general formula (I) of the component (B). May be used alone or in combination of two or more. Further, one or more kinds of the component (a) and one or more kinds of the component (b) may be used in combination.

In the harmful microbial eradication agent of the present invention, the content of the component (C) used as desired is 1 to 100 with respect to the total amount of the components (A) and (B).
A range of weight% is preferred. When the content of the component (C) is within the above range, an excellent synergistic effect can be obtained. If this content deviates from the above range, the effect of improving the efficacy against bacteria and mold will not be sufficiently exhibited. The particularly preferable content of the component (C) is (A) because it exerts an excellent synergistic effect and exhibits high efficacy against both bacteria and mold.
It is in the range of 1 to 50% by weight based on the total amount of the components and the component (B).

Preferred as the harmful microbial eradication agent of the present invention are 1,2-bisbromoacetoxyethane, 1,2-bisbromoacetoxybutene and 1,2 as the component (A).
At least one selected from 2-bisbromoacetoxypropane as the component (B) is 3,3,4,4-
Using tetrachlorotetrahydrothiophene-1,1-dioxide as the component (C), 2,2-dibromo-2-nitroethanol, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane- 1,
3-diol, 1,1-dibromo-1-nitro-2-acetoxyethane and 2-bromo-2-nitro-1,3-
Those containing at least one selected from diacetoxypropane, and particularly preferred one is 1,2-bisbromoacetoxyethane as the component (A),
The component (B) contains 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, and the component (C) contains 2,2-dibromo-3-nitrilopropionamide.

The harmful microorganism eradicating agent of the present invention is basically prepared by uniformly mixing the above-mentioned component (A), component (B) and optionally component (C). Typically, it is used as a solvent solution.

Examples of the solvent that can be used here include alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents and the like, among which alkylene glycol, dialkylene glycol, dialkylene glycol monoalkyl ether and the like. The glycol-based solvent is preferred, and ethylene glycol, diethylene glycol, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and dipropylene glycol are particularly preferred. Also, propylene carbonate, ethylene carbonate,
γ-butyrolactone, N-methylpyrrolidone, tetrahydrofurfuryl alcohol and the like may be used. These solvents may be used alone or in combination of two or more.

There are no particular restrictions on the mode of use of the harmful microbial eradication agent of the present invention, and various methods can be adopted, and for example, it may be used by supporting it on any carrier.

The amount of the harmful microbial eradication agent of the present invention to be added varies depending on the concentration of the microorganisms. In the case of water systems in the field, it is about 1 to 50 ppm based on the total amount of both components, and in the field of water-based paints, glues, leather, etc., it is about 20 to 400 ppm. Also,
In the three-component type antibacterial agent of the component (A), the component (B), and the component (C), based on the total amount of the three components, in the case of a water-based system in the pulp and paper industry, about 1 to 30 ppm, an aqueous paint,
In the field of glue, leather, etc., it is about 15 to 300 ppm, and a good antibacterial effect can be obtained in this range.

If desired, stabilizers, surfactants and the like can be added to the harmful microorganism erasing agent of the present invention within a range that does not impair the object of the present invention. Surfactants have the effect of increasing solubility.

[0031]

INDUSTRIAL APPLICABILITY The harmful microbial eradication agent of the present invention exerts a unique synergistic effect which cannot be predicted from the individual components by combining two or three specific antibacterial agents. , The range of microorganisms that can be sterilized is greatly expanded and has an extremely broad antibacterial spectrum, exhibits excellent antibacterial and antifungal effects, and can effectively suppress the growth of various microorganisms, and High stability.

The harmful microbial eradication agent of the present invention is used for water-based paints and paper coating liquids, in addition to water-based water systems in the paper and pulp industry, such as white water in the papermaking process and circulating cooling water in various industrial fields. It is preferably used in the fields of metal working oils such as latex, polymer emulsion, printing paste, cutting oil, adhesives, leather and wood.

[0033]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 5 and Comparative Examples 1 and 2 A harmful microorganism erasing agent having the composition shown in Table 1 was prepared, and the performance was tested as follows.

(1) Bacterial growth prevention test and slime generation prevention test in white water in the papermaking process In the papermaking process of a papermaking factory, each antibacterial agent was added to the whitewater pit in an amount of 1
The number of the microorganisms in the white water was measured by adding the drug excluding the solvent to the concentration in water of 20 ppm over 7 days so that the concentration in water was 20 ppm over 2 hours. As a test method, a white water sample was diluted with sterilized water, and a certain amount of this was put into a petri dish, poured into a dissolved Waxman agar medium, mixed, and solidified into a flat plate. Microbial colonies generated after culturing in an incubator (32 ° C.) for 2 days were measured with a colony counter. In addition, the number of paper breaks during papermaking was also measured to confirm the effect of preventing slime generation. The results are shown in Table 2.

(2) Bacterial Growth Prevention Test in Papermaking Coating Liquid A broth liquid medium and a coating liquid which has been spoiled in advance are added to a starch-based coating liquid for papermaking and stirred to give a drug concentration of 300 ppm excluding the solvent. Each antibacterial agent was added as follows. After this was stored in a thermostat at 32 ° C. for 5 days, the number of viable bacteria in each coating solution was measured. The results are shown in Table 2.

(3) Bacterial Growth Prevention Test in Latex A broth liquid medium and a previously putrefactive latex were added to the latex and stirred, and each antibacterial agent was added so that the concentration of the drug excluding the solvent was 300 ppm. After storing this in a thermostat at 32 ° C. for 5 days, the number of viable bacteria in the latex was measured. The results are shown in Table 2.

(4) Bacterial growth prevention test in cutting oil A broth liquid medium and cutting oil which has been spoiled in advance are added to the cutting oil, and the mixture is stirred, and the solvent concentration is 300 p except for the solvent.
Each antibacterial agent was added so that it would be pm. After storing this in a thermostat at 32 ° C. for 5 days, the number of viable bacteria in the cutting oil was measured. The results are shown in Table 2.

[0039]

[Table 1]

(A): 1,2-bisbromoacetoxyethane (B): 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (C) -1: 2,2-dibromo-3 -Nitrilopropionamide (C) -2: Caisson LX PLUS (trade name, manufactured by Rohm and Haas Co.), 5-chloro-2-methyl-4-isothiazolin-3-one as a main component, and other 2-methyl-4 -Isothiazolin-3-one-containing water-soluble fungicide (C) -3: 2,2-dibromo-2-nitroethanol Solvent: ethylene glycol

[0041]

[Table 2]

(Note) Number of paper breaks: The number of paper breaks for 7 days under the condition of 1000 m / min. From these results, the harmful microbial eradication agent of the present invention has excellent antibacterial and antifungal properties, and when added to white water in the papermaking process, the number of paper breaks is reduced, resulting in improved work efficiency.

Claims (4)

[Claims] 1. (A) a halogenoacetic acid ester, and (B)
An agent for eradicating harmful microorganisms, which comprises 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. 2. (A) a halogenoacetic ester, and (B)
3,3,4,4-Tetrachlorotetrahydrothiophene-1,1-dioxide, (C) (a) isothiazolone compound and (b) general formula (Wherein X ¹ is a halogen atom, Y is a nitro group or a cyano group, R ¹ and R ² are a halogen atom, a nitro group, a cyano group, a hydroxyl group, an aminocarbonyl group or a substituted or unsubstituted alkyl group, respectively. , Which may be the same or different from each other), containing at least one selected from the compounds represented by the formula (1). 3. The mixing ratio of the component (A) and the component (B) is 100: 1 to 1: 100 on a weight basis.
Or the harmful microorganism erasing agent according to 2. 4. The harmful microorganism eradicating agent according to claim 2 or 3, wherein the content of the component (C) is 1 to 100% by weight based on the total amount of the components (A) and (B).