JPH0912412A - Agent for exterminating harmful microorganism - Google Patents

Abstract

PURPOSE: To obtain a new agent for exterminating harmful microorganisms, composed of a combination of two or three kinds of specific agents having antimicrobial power, exhibiting characteristic synergistic effect unexpectable from the individual components and having excellent antibacterial and antifungal effects. CONSTITUTION: This extermination agent is a combination of (A) methylene bisthiocyanate of formula I and (B) 3,3,4,4-tetrachlorotetrahydrothiopene-1,1- dioxide or formula II or further (C) a halocyanoacetamide derivative of formula III (R<1> is H, a halogen or an alkyl; R<2> is H or an alkyl; X is a halogen). The compounding weight ratio of the component A and the component B is preferably 10:1 to 1:10. The amount of the component C is preferably 3-1, 250wt.% based on the sum of A and B. The harmful microorganism extermination agent has a broad antimicrobial spectrum and excellent effect for suppressing the proliferation of various harmful microorganisms and is suitable for the use in a water system of paper and pulp industry and various other industrial fields.

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 sterilization and fungicidal effects, it also has an excellent effect of suppressing the growth of various harmful microorganisms, including a water system in the pulp and paper industry, and a harmful microorganism erasing agent that is preferably used in various industrial fields. is there.

[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 fluids, latex, polymer emulsions, printing pastes, adhesives, metalworking oils such as cutting oils, leather, and wood, microorganisms harmful to them easily propagate, which results in productivity and quality. Is causing the decrease of. Especially in water systems in the pulp and paper industry, slime is generated due to the proliferation of bacteria, filamentous fungi, and yeasts, and the water channel in which the pulp slurry flows, especially the rough wall surface where the slurry contacts, chests, flow boxes, transportation pipes, etc. Slime is deposited and formed in a place where the flow velocity of the pipe slurry becomes small and stagnates.

The slime is often detached, causes paper scraps and stains on pulp and paper products, and causes various damages due to the growth of microorganisms. The occurrence of such a trouble becomes a serious problem especially when using a high-speed machine, resulting in a significant decrease in productivity and an economic loss.

Further, for example, the proliferation of microorganisms in a circulating water system for cooling such as metalworking oils impairs the cooling performance and emulsifying property, and also produces a bad odor to deteriorate the working environment, which is an undesirable phenomenon in public health. cause. In addition, other problems caused by the proliferation of harmful microorganisms include water-based paints, paper coating solutions, polymer latex, papermaking pulp,
It is also found in industrial products such as glue, leather, wood, and metalworking oils.

By the way, as the chemicals for suppressing or controlling the generation of harmful microorganisms in the above-mentioned water systems and industrial products, for example, organometallic compounds and quaternary ammonium salt compounds have been used so far. The compounds are toxic to the human body, emit an offensive odor and an offensive odor, and cause undesirable phenomena such as foaming.
In addition, 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.

As a means for avoiding such a problem,
For example, methylenebisthiocyanate (Japanese Patent Publication No. 57-53)
323), 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (US Pat. No. 2,957,887), halocyanoacetamide derivative [“Applied Microbiology (App
l. Microbiology) ", 24, 58
1 to 4 (1972)] and the like are known.

However, since the range of harmful microorganisms that can be sterilized is limited and a broad spectrum of antibacterial spectrum cannot be obtained, the applicable range is limited, and water containing many kinds of harmful microorganisms such as white water is limited. On the other hand, the bactericidal effect is insufficient, and the fungicidal effect and the effect of suppressing the growth of various microorganisms are also difficult, so that they are not necessarily satisfactory as harmful microbial eradication agents.

[0008]

Under the circumstances, the present invention has a broad antibacterial spectrum, exhibits excellent bactericidal and fungicidal effects, and suppresses the reproduction of various harmful microorganisms. It was made for the purpose of providing an excellent microbial eradication agent.

[0009]

Means for Solving the Problems The present inventors have conducted various studies to develop a harmful microbial eradication agent having a wide range of application, and as a result, have been used the conventional methylenebisthiocyanate, 3,3,4. It has been found that the object can be achieved by combining 4-tetrachlorotetrahydrothiophene-1,1-dioxide and optionally a halocyanoacetamide derivative, and the present invention has been completed based on this finding.

Thus, the present invention relates to (A) methylenebisthiocyanate, (B) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and optionally (C) the general formula

Embedded image (R ¹ in the formula is a hydrogen atom, a halogen atom or a lower alkyl group, R ² is a hydrogen atom or a lower alkyl group, and X is a halogen atom) and a harmful compound characterized by containing a halocyanoacetamide derivative It provides a microbial eradication agent.

Here, the harmful microorganism eradicating agent means the ability to suppress the normal growth of microorganisms that cause some damage, such as bacteria, fungi and algae, in the methods, devices and equipment used for maintaining the living environment and industrial production. And a bactericide, a fungicide, a sterilizer, a growth inhibitor, a remover and the like.

In the harmful microorganism eradication agent of the present invention,
The methylenebisthiocyanate used as the component (A) is represented by the formula CH ₂ (SCN) ₂ (II), and 3,3,4,4-tetrachlorotetrahydrothiophene-used as the component (B). 1,1-dioxide 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 in the range of 10: 1 to 1:10 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 growth inhibitory power and bactericidal activity of bacteria are insufficient, while the ratio of the (A) component When the ratio is more than the above range [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 a high bactericidal effect against both bacteria and mold, the particularly preferable mixing ratio of the component (A) and the component (B) is in the range of 5: 1 to 1: 5. is there.

In the harmful microbial eradication agent of the present invention, the above-mentioned components (A) and (B) may be used, if desired,
The component (C) may contain the halocyanoacetamide derivative represented by the general formula (I).

Examples of the halogen atom of R ¹ in the general formula (I) include Cl, Br and the like, and examples of the lower alkyl group include a methyl group and an ethyl group. Further, examples of the lower alkyl group of R ² include a methyl group and an ethyl group, while
Examples of the halogen atom for X include Cl and Br. As the component (C), 2,2-dibromo-3-nitrilopropionamide in which R ¹ and X are both Br and R ² is a hydrogen atom is preferable because of excellent bactericidal properties, and Examples thereof include chloro-3-nitrilopropionamide, 2-bromo-3-nitrilopropionamide, 2,2-dichloro-3-nitrilopropionamide, N-methyl-2,2-dibromo-3-nitrilopropionamide and the like. These may be used alone or in combination of two or more.

In the harmful microbial eradication agent of the present invention, the mixing ratio of the component (C) is preferably in the range of 3 to 1250% by weight based on the total amount of the components (A) and (B). When the blending ratio of the component (C) is within the above range, an excellent synergistic effect can be obtained. If the blending ratio is less than 3% by weight, the bactericidal activity against bacteria is insufficient, and 1250
If it exceeds 5% by weight, the bactericidal activity against mold is rather lowered, which is not preferable. From the point of exhibiting excellent synergistic effect and showing high bactericidal effect against both bacteria and mold,
A particularly preferable mixing ratio of the component (C) is in the range of 50 to 500% by weight based on the total amount of the component (A) and the component (B).

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). Generally, 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 them, alkylene glycol, dialkylene glycol, dialkylene glycol monoalkyl ether, etc. 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.

The use mode of the harmful microorganism erasing agent of the present invention is not particularly limited, and various methods can be adopted, and for example, it may be supported on any carrier and used.

The amount of the harmful microbial eradication agent of the present invention to be added varies depending on the concentration of the microorganism, but in the case of the two-component type bactericide of the component (A) and the component (B), it is generally used in the pulp and paper industry. 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 bactericide 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 invention. Surfactants have the effect of increasing solubility.

[0022]

INDUSTRIAL APPLICABILITY The harmful microbial eradication agent of the present invention exhibits a unique synergistic effect which cannot be predicted from each individual component by combining two or three specific antibacterial agents, The range of microorganisms that can be sterilized is greatly expanded to have an extremely wide range of antibacterial spectrum, while exhibiting excellent bactericidal and fungicidal effects, and effectively suppressing the growth of various microorganisms.

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

[0024]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

Examples 1 to 5 and Comparative Examples 1 to 3 The harmful microorganism eradicating agents having the composition shown in Table 1 were prepared, and the following tests were conducted for their performance.

(1) Bacterial growth prevention test and slime generation test in white water in the papermaking process In the papermaking process of a paper mill, each bactericide was applied to a white water bit for 2 hours and 3 times in a day to remove the solvent. It was added for 7 days so that the concentration in water was 20 ppm, and the number of microorganisms in white water was measured. As a test method, a white water sample was diluted with sterilized water, and a certain amount of this was taken in 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. Table 2 shows the results.

(2) Bacterial growth prevention test in paper-making coating liquid A broth liquid medium and a pre-rotted coating liquid were added to a starch-made coating liquid for paper-making and stirred to bring the concentration of the drug excluding the solvent to 300 ppm. Each fungicide was added so that After this was stored in a thermostat at 32 ° C. for 5 days, the number of viable bacteria in each coating solution was measured. Table 2 shows the results. Table 2
The test results for those to which no fungicide was added are also shown as blanks.

(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. Table 2 shows the results.

(4) Bacterial growth prevention test in cutting oil A broth liquid medium and cutting oil that has been putrefaction 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. Table 2 shows the results.

[0030]

[Table 1]

(A): Methylenebisthiocyanate (B): 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (C): 2,2-dibromo-3-nitrilopropionamide Solvent: ethylene Glycol

[0032]

[Table 2]

(Note) Paper breakage collection: The number of paper breaks per hour under the condition of 1000 m / min. From these results, the harmful microorganism 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.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area A01N 37:34)

Claims (4)

[Claims] 1. A harmful microorganism eradicating agent comprising (A) methylenebisthiocyanate and (B) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. 2. (A) Methylenebisthiocyanate,
(B) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and (C) the general formula: (R ¹ in the formula is a hydrogen atom, a halogen atom or a lower alkyl group, R ² is a hydrogen atom or a lower alkyl group, and X is a halogen atom) and a harmful compound characterized by containing a halocyanoacetamide derivative Microbial eradication agent. 3. The harmful microorganism eradication agent according to claim 1, wherein the mixing ratio of the component (A) and the component (B) is in the range of 10: 1 to 1:10 on a weight basis. 4. The harmful microorganism eradicating agent according to claim 2, wherein the blending ratio of the component (C) is in the range of 3 to 1250% by weight based on the total amount of the components (A) and (B). .