JP2891622B2 - Industrial antibacterial agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a unique synergistic effect of being highly stable, capable of greatly expanding the range of microorganisms that can be prevented, having an extremely wide antibacterial spectrum, and having an excellent antibacterial effect. In particular, water systems in the pulp and paper industry, for example, various water systems such as drainage from the papermaking process so-called white water and circulating cooling water in various industrial fields, water-based paints prepared using industrial water, The present invention relates to a novel industrial antibacterial agent which is suitably used in the fields of metalworking oils such as coating liquids for paper, latex, polymer emulsions, printing pastes, adhesives, cutting oils, and leather.

[0002]

2. Description of the Related Art Conventionally, in the fields described above,
Microorganisms that are harmful to them tend to multiply, which causes a decrease in productivity and quality. In particular, in the water system in the pulp and paper industry, bacteria, filamentous fungi, slime is generated due to the increased propagation of yeasts, water channels through which the pulp slurry flows, especially places with rough wall surfaces where the slurry contacts, chests, flow boxes, transport pipes, In other places where the flow velocity of the pipe slurry becomes small and stagnates, slime is attached and formed. This slime is often detached, causes paper breakage and contamination of paper pipe products, and causes various obstacles due to the propagation of microorganisms. The occurrence of such an obstacle becomes a serious problem, especially when a high-speed machine is used, and causes a significant decrease in productivity and economic loss. In addition, for example, the proliferation and growth of microorganisms in a circulating water system for cooling such as metalworking oils inhibits cooling performance and emulsifying properties,
In addition, it causes unpleasant phenomena in public health, such as generating odor and deteriorating the working environment. Further, other obstacles due to the propagation of harmful microorganisms are also found in industrial products such as water-based paints, coating solutions for paper, polymer latex, pulp for papermaking, glue, leather, and metalworking oils.

[0003] By the way, as agents for suppressing or controlling the generation of harmful microorganisms in the water system or the industrial products, there have hitherto been mentioned, for example, organometallic compounds, organochlorine compounds, organic sulfur compounds, quaternary ammonium salts. Although these compounds have been used, these compounds are toxic to the human body, emit bad smells and unpleasant odors, and further cause undesirable phenomena such as foaming. In addition, when these control agent-containing water systems are discharged into general rivers or the sea, they have an adverse effect on fish and shellfish and cause environmental conservation problems.

[0004] As a compound which can avoid such a problem, for example, an isothiazolone compound (Japanese Patent Publication No. 54-23 / 1979)
968), dibromonitrilopropionamide-based compounds [“Applied Microbiology (App
l. Microbiology), Vol. 24, No. 58
1-4, (1972)], 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (U.S. Pat. No. 2,957,887), and the like. All have specific actions, restrict the types of microorganisms that can be bactericidal, have insufficient antibacterial effects on water containing various types of microorganisms such as white water, and have difficulty in stability. Therefore, they are not always satisfactory as industrial antibacterial agents.

Further, a combination of two or more compounds having a fungicidal action in order to enhance the fungicidal effect, for example, 2,2-dibromo-3-nitrilopropanamide and 3,3
3,4,4-tetrachlorotetrahydrothiophene-
Compositions comprising 1,1-dioxide (U.S. Pat.
No. 928,198), a composition containing an isothiazolone complex compound and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (JP-A-62-1).
No. 48409), a composition comprising dithiol and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (Japanese Patent Publication No. 3-44042), a composition comprising dithiol and dibromonitrilopropionamide (Japanese Patent Publication No. 1-2121) is known. However, these are each limited in the range of microorganisms that can be bactericidal and cannot provide a broad antibacterial spectrum, so that the range of application is inevitably limited.

[0006]

SUMMARY OF THE INVENTION Under such circumstances, the present invention can greatly expand the range of microorganisms which are highly stable and can prevent bacteria, have an extremely wide antibacterial spectrum, and have an excellent antibacterial spectrum. The purpose of the present invention is to provide an industrial antibacterial agent that exhibits an antibacterial effect.

[0007]

The present inventors have conducted various studies to develop an industrial antibacterial agent having a wide range of application. As a result, the present inventors have found that nitrilopropionamide, which has been conventionally used as an industrial antibacterial agent, has been developed. It has been found that the object can be achieved by combining 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide with a specific dithiol compound for a compound. Was reached.

That is, the present invention relates to (A) a compound represented by the general formula (I)

Embedded image (Wherein R ¹ is a hydrogen atom, a halogen atom or an alkyl group, R ² is a hydrogen atom or an alkyl group, and X is a halogen atom), (B) 3,3,4,4 -Tetrachlorotetrahydrothiophene-1,1-dioxide and (C) a compound of the general formula (I
I)

Embedded image (Wherein R ³ and R ⁴ in the formulas are each a hydrogen atom, a halogen atom or an alkyl group) and a dithiol compound represented by the formula:

The nitrilopropionamide compound used as the component (A) of the present invention is represented by the general formula (I):
As the halogen atom of R ^{3 in} the formula, for example, C 3
l, Br, etc., the alkyl group includes, for example, a methyl group and an ethyl group, and the alkyl group of R ² includes, for example, a methyl group, an ethyl group, and the like. , Br and the like, and 2,2-dibromo-3-nitrilopropionamide, in which both R ¹ and X are Br, is preferred because of its excellent bactericidal activity. In addition, as the nitrilopropionamide compound of the general formula (I), for example, 2-chloro-3-nitrilopropionamide, 2-bromo-3-
Nitrilopropionamide, 2,2-dichloro-3-nitrilopropionamide, N-methyl-2,2-dibromo-3-nitrilopropionamide and the like can be mentioned.
These may be used alone or in combination of two or more.

Next, the component (B) of the present invention,
3,4,4-tetrachlorotetrahydrothiophene-
1,1-dioxide has the chemical formula (III)

Embedded image Is represented by

Next, the component (C) of the present invention,
The 2-dithiol compound is represented by the general formula (II):
Examples of the halogen atom among R ¹ and R ^{2 in} the formula include, for example, Cl and Br, and examples of the alkyl group include, for example, a methyl group and an ethyl group, and R ¹ and R ² are the same as each other. Although they may be present or different from each other, it is particularly preferable that both are Cl because of their excellent bactericidal properties. 1,2- of the general formula (II)
Examples of the dithiol compound include, for example, 4,5-dibromo-
1,2-dithiol, 4,5-dichloro-1,2-dithiol, 4-chloro-5-bromo-1,2-dithiol, 4,5-dimethyl-1,2-dithiol, 4,5-
Diethyl-1,2-dithiol and the like. These may be used alone or in combination of two or more.

In the antibacterial agent of the present invention, (A) component 1
It is sufficiently synergistic to mix 10 to 80 parts by weight, preferably 20 to 70 parts by weight of component (B) and 10 to 70 parts by weight, preferably 15 to 60 parts by weight of component (C) per 100 parts by weight. It is preferable because effects can be obtained. If any of these components deviates from this range, a sufficient synergistic effect will not be exhibited. That is, if the amount of the component (A) is too small, the bactericidal activity against bacteria decreases, and if it is too large, the bactericidal activity against mold decreases. When the amount of the component (B) is too small, the ability to inhibit the growth of bacteria is reduced. When the amount is too large, the bactericidal power to bacteria is reduced. When the amount of the component (C) is too small, the bactericidal activity against fungi decreases, and the ability to inhibit the growth of bacteria and mold decreases. When the amount is too large, the bactericidal activity against bacteria and mold decreases.

The bactericidal agent of the present invention is basically prepared by uniformly mixing the above three components (A), (B) and (C). solution,
It is used as an emulsified dispersion or the like. Examples of the solvent that can be used here include alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, and the like.
Among them, glycol solvents such as alkylene glycol, dialkylene glycol, dialkylene glycol monoalkyl ether and the like are preferable, and ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol are particularly preferable. Examples of the emulsifying dispersant include surfactants such as anionic surfactants and nonionic surfactants. Surfactants also have the effect of increasing solubility. The antibacterial agent of the present invention may be used by being supported on any carrier, and there is no particular limitation on the mode of use, and various methods can be adopted.

The amount of the antibacterial agent to be added varies depending on the concentration of microorganisms. Generally, in the case of a water system in the field of the pulp and paper industry, the components (A), (B) and (C) are used. ) 0.01-100 pp based on the total amount of components
m, 1-500p for water paint, glue, leather etc.
pm, and a good bactericidal effect can be obtained in this range. To the antibacterial agent of the present invention, it is possible to add a stabilizer, a surfactant and the like within a range that does not inhibit the object of the present invention.
Surfactants have the effect of increasing solubility.

[0015]

The antibacterial agent of the present invention can be obtained not only by individual components but also by a combination of these two components by combining the three components of specific nitrilopropionamide, chlorotetrahydrothiophene dioxide and dithiol. In addition, a unique synergistic effect that cannot be expected from these, that is, a high stability, can greatly expand the range of microorganisms that can be prevented, has an extremely wide antibacterial spectrum, and has an excellent antibacterial effect In particular, water systems in the pulp and paper industry, such as wastewater from the papermaking process, so-called white water and circulating cooling water in various industrial fields, as well as water-based paints and paper coatings Liquid, latex, polymer emulsion, printing paste, metalworking oils such as cutting oil, adhesives, leather, etc. It is suitable.

[0016]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Examples 1 to 3 and Comparative Examples 1 to 3 Bactericidal agents composed of compositions having the respective compositional components and the amounts (in parts by weight) shown in Table 1 were prepared.

[0017]

[Table 1]

Reference Examples The following tests were performed on the antibacterial agents obtained in the respective Examples and Comparative Examples. (1) Bacterial growth prevention test and slime generation prevention test in wastewater after papermaking process In the papermaking process of a paper mill, each antibacterial agent is added to a white water bit.
The water concentration is 20pp for 2 hours and 3 times a day.
m, and the number of microorganisms in the white water was measured. In the test method, a white water sample was diluted with sterilized water, a predetermined amount thereof was taken in a petri dish, a dissolved waxman agar medium was injected, mixed, and solidified into a 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 antibacterial effect. Table 2 shows the results.

(2) Test for Preventing Bacterial Proliferation in Coating Solution for Papermaking A bouillon liquid medium and a previously spoiled coating solution were added to a starch-based coating solution having a pH of 10.0, and the mixture was stirred.
A bactericidal agent adjusted to a concentration was added. This is 3
After storing in a 2 ° C. incubator for 5 days, the number of viable bacteria in each coating solution was measured. Table 2 shows the results.

(3) Stability test Each antibacterial agent sample was stored in a constant temperature room at 40 ° C., and a part of each sample was sampled daily, and subjected to liquid chromatography.
The residual concentrations of the component (A) and / or the component (B) and / or the component (C) were measured, and their residual rates are shown in Table 3. The residual rate was calculated by the following equation.

(Equation 1) (X in the formula indicates the content of each component at the time of preparation, and X 'indicates the content of each component after 30 days.)

(4) Antibacterial spectrum test A certain amount of various microorganisms shown in Table 4 was taken, diluted with a certain amount of sterilized water, and this certain amount was taken in a test tube, and each of the antibacterial agent samples shown in Table 1 was placed therein. Is 2.5 ppm, 5 ppm, 10 pp
m, 20 ppm, 40 ppm, and 80 ppm, and contacted in a thermostat (32 ° C.) for 60 minutes. Then, a fixed amount was taken in a petri dish, and a dissolved waxman agar medium was injected, and mixed. And solidified into a flat plate.
Microbial colonies generated after culturing in an incubator (32 ° C.) for 2 days were visually compared with blanks (without adding a drug), and the minimum microbial bactericidal concentration was determined according to the state of the microbial colonies generated. Table 4 shows a list of the resulting antibacterial activities.

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

From these results, all of the antibacterial agents of the examples of the present invention exhibited excellent effects of preventing bacterial growth and slime generation in the wastewater of a paper mill compared with those of the comparative examples. It shows that the coating liquid for use has an excellent antibacterial action, has an extremely broad antibacterial spectrum, and has a high stability like a two-component system.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI A01N 37:34 43:10) (56) References JP-A-5-70306 (JP, A) JP-A-6-40811 (JP, A) JP-A-61-236706 (JP, A) JP-A-6-32702 (JP, A) JP-A-7-173004 (JP, A) JP-A-63-88103 (JP, A) JP-A-6-24910 (JP, A) (58) Fields surveyed (Int. Cl. ⁶ , DB name) A01N 37/34 101 A01N 43/10 A01N 43/26 CAPLUS (STN)

Claims (3)

(57) [Claims] (A) General formula (1) Wherein R ¹ is a hydrogen atom, a halogen atom or an alkyl group, R ² is a hydrogen atom or an alkyl group, and X is a halogen atom, and (B) 3,3,4, 4-tetrachlorotetrahydrothiophene-1,1-dioxide and (C) a general formula (Wherein R ³ and R ⁴ in the formulas are each a hydrogen atom, a halogen atom or an alkyl group). 2. The industrial antibacterial agent according to claim 1, wherein 10 to 80 parts by weight of the component (B) and 10 to 70 parts by weight of the component (C) are mixed per 100 parts by weight of the component (A). 3. The industrial antibacterial agent according to claim 1, further comprising a surfactant.