JP2908976B2 - 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.

[0003] The slime is often desorbed, causing not only paper breakage and contamination of pulp and paper products, but also causes various obstacles due to propagation of microorganisms.

[0004] 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.

[0005] In addition, the proliferation and growth of microorganisms in a circulating water system for cooling metal working oils and the like is an undesirable phenomenon in public health, such as impairing the cooling performance and emulsifying properties, and generating a bad smell and deteriorating the working environment. cause.

Further, other obstacles due to the propagation of harmful microorganisms include water-based paints, coating solutions for paper, polymer latex,
It is also found in industrial products such as paper pulp, glue, leather, and metalworking oils.

[0007] 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, organic chlorine 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.

As a compound which can avoid such a problem, for example, an isothiazolone compound (JP-B-54-23)
968), a nitrilopropionamide-based compound [“Applied Microbiology (Appl. Mi)
24, 581-4 (1972)], 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (U.S. Pat. No. 2,957,887). These are known, but all of them are specific in action, the types of microorganisms that can be prevented are restricted, and their antibacterial effect is insufficient against water containing various types of microorganisms such as white water. In addition, there are difficulties in the stability, so that 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-tetrachlorotetrahydrothiophen-1,1-dioxide (Japanese Patent Publication No. 3-44042),
Composition containing dithiol and dibromonitrilopropionamide (Japanese Patent Publication No. Hei 1-220121) and composition containing dithiol and an isothiazolone compound (JP-A 2-2)
No. 58703).

[0010] However, since the range of microorganisms that can be bactericidal is limited in each case, and a broad antibacterial spectrum cannot be obtained, the range of application is inevitably limited.

[0011]

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.

[0012]

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. For the compound, a specific dithiol, a specific isothiazolone compound and optionally 3,3,4
It has been found that the object can be achieved by combining 4-tetrachlorotetrahydrothiophene-1,1-dioxide, and the present invention has been accomplished based on this finding.

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) a general formula

Embedded image (Wherein R ³ is a hydrogen atom or a hydrocarbon group, and R ⁴ and R ⁵ are a hydrogen atom or a halogen atom, which may be the same as or different from each other). Isothiazolone compounds represented by the general formula (C)

Embedded image (Wherein R ⁶ and R ⁷ are a hydrogen atom, a halogen atom or an alkyl group, and these may be the same as each other;
An industrial germicidal agent characterized by containing a dithiol compound represented by the formula (I) which may be different from the above, and optionally (D) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. To provide.

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 ^{1 in} the formula, for example, C 1
l, Br, etc., and the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc., and the alkyl group of R ² is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc. Examples of the halogen atom for X include Cl, Br and the like. In particular, 2,2-dibromo-3-nitrilopropionamide, in which both R ¹ and X are Br, is preferable because of its excellent bactericidal activity. Other examples of the nitrilopropionamide compound of the general formula (I) include 2-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.

Next, the isothiazolone compound used as the component (B) of the present invention is represented by the general formula (II), wherein the hydrocarbon group of R ³ is a methyl group, an ethyl group, propyl group, butyl group, an alkyl group, a cyclohexyl group, octyl group, cycloalkyl group and the like, such as a cyclopentyl group, a halogen atom of R ⁴ and R ⁵ Cl, Br and the like, respectively, also R ⁴ And R ⁵ may be the same as or different from each other, and particularly include those in which both are Cl, for example, 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one and the like. It is preferable because of its excellent antifungal effect. Examples of the isothiazolone compound of the general formula (II) include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazoline-3-one
ON, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 5- Chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-t-octyl-4-
Isothiazolin-3-one and the like. These may be used alone or in combination of two or more.

[0016] Next, (C) used as component 1,2 dithiol compound of the present invention is represented by the general formula (III), the halogen atom of ^{R 6} and ^{R 7} in formula e.g. Cl, Br and the like, and examples of the alkyl group include a methyl group and an ethyl group. R ⁶ and R ⁷ may be the same or different from each other. Both are preferably Cl because of their excellent bactericidal properties. General formula (III)
Examples of the 1,2-dithiol compound include 4,5-dithiol compounds
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 a sufficiently satisfactory synergy to mix 1 to 200 parts by weight, preferably 20 to 120 parts by weight, of component (B) and 1 to 100 parts by weight, preferably 15 to 80 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 bactericidal activity against mold decreases, and when it is too large, the bactericidal activity against bacteria and mold decreases. 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.

In the antibacterial agent of the present invention, in addition to the above components (A), (B) and (C), if desired, 3,3,4,4-tetrachlorotetrahydrotetrahydrofuran may be used as component (D). Thiophene-1,1-dioxide can be included. The compound of the component (D) has the chemical formula (I)
V)

Embedded image Is represented by

When the component (D) is blended, the content thereof is 1 to 200 parts by weight, preferably 2 parts by weight, per 100 parts by weight of the total of the components (A), (B) and (C).
It is preferable to select so as to be in the range of 0 to 150 parts by weight. If the ratio is too small, the ability to inhibit the growth of bacteria will decrease, and if it is too large, the bactericidal activity against bacteria will decrease.

The antibacterial agent of the present invention is basically composed of the above-mentioned three components (A), (B) and (C) or four components obtained by adding the (D) component used as required. It is prepared by mixing uniformly, but is generally used as a solvent solution.

The solvents which can be used here include triol solvents, glycol solvents, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, etc., among which glycerin, trimethylolpropane, etc. Triol compounds, alkylene glycols, dialkylene glycols, glycol solvents such as dialkylene glycol monoalkyl ethers are preferred, particularly glycerin or trimethylolpropane,
A mixed solvent of at least one selected from ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol as the component (A);
The composition containing the component, the component (C) and the component (D) used as desired can be adjusted to a desired concentration, which is preferable. These solvents may be used alone or in combination of two or more.

The antibacterial agent of the present invention may be used by being supported on an arbitrary carrier, and there are no particular restrictions on the mode of use, and various methods can be employed.

The amount of the antibacterial agent to be added varies depending on the concentration of microorganisms. In general, in the case of a water system in the pulp and paper industry, the components (A), (B) and (C) are used. 1) 100 p based on the total amount of the three components
pm, water-based paint, glue, leather, etc., in the range of 10 to 500 ppm based on the total amount of the above three components, and component (D) used as desired, component (A), component (B) and component (C) And 1 to 50 ppm based on the total amount of water-based paint, glue, leather and the like in the field of 25 to 300 pp.
m, and a good antibacterial effect can be obtained in this range. Addition of a stabilizer, a surfactant or the like to the germicidal agent of the present invention may be carried out without impairing the object of the present invention, and the surfactant has an effect of increasing the solubility.

[0025]

According to the present invention, the antibacterial agent is a specific nitrilopropionamide, isothiazoline or dithiol.
By combining the component or chlorotetrahydrothiophene dioxide with the component, not only individual components but also a combination of these two components cannot be obtained at all, and a unique synergistic effect which cannot be expected from these components, that is, high stability, Moreover, the range of microorganisms that can be germ-proofed can be greatly expanded, it has an extremely broad antibacterial spectrum, and has a synergistic effect of exhibiting an excellent bactericidal effect. And water pollution in paper pulp industry, such as waste water from paper making process, so-called white water, and circulating cooling water in various industrial fields. Liquid, latex, polymer emulsion, printing paste, metalworking oils such as cutting oil, adhesives,
It is suitable for use in fields such as leather.

[0026]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Examples 1 to 6 and Comparative Examples 1 to 6 Bactericidal agents composed of compositions having the respective components shown in Table 1 and the amounts (in parts by weight) shown in Table 1 were prepared.

[0027]

[Table 1]

* 1 to * 6 in the table have the following meanings. * 1 2,2-Dibromo-3-nitrilopropionamide * 2 5-Chloro-2-methyl-4-isothiazoline-
3: 1 mixture of 3-one and 2-methyl-4-isothiazolin-3-one * 3 4,5-dichloro-1,2-dithiol * 4 diethylene glycol monomethyl ether * 5 ethylene glycol * 6 glycerin

Reference Example 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 the papermaking process In the papermaking process of a paper mill, each antibacterial agent becomes 20 ppm in a white water bit for 2 hours and 3 times in a day. For 7 days, and the number of microorganisms in the white water was measured. The test method is to dilute a white water sample with sterile water, take a certain amount of this in a petri dish,
The melted 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 Growth 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 to give 300 ppm.
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) and / or the component (D) were measured, and their residual ratios are shown in Table 3. The residual rate was calculated by the following equation. Residual rate (%) = (X ′ / X) × 100 (in the formula, X represents the content of each component in the preparation, and X ′ represents the content of each component after 30 days)

(4) Antibacterial spectrum test A certain amount of each of the 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. 5 ppm, 10 ppm, 20 pp
m, 40 ppm, and 80 ppm, and contacted in a thermostat (32 ° C.) for 60 minutes. A fixed amount was taken in a petri dish, and a dissolved waxman agar medium was poured, mixed, and mixed. And solidified. 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.

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

From these results, all of the antibacterial agents of the examples of the present invention exhibited excellent antibacterial growth and slime generation in drainage 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.

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁶ identification code FI A01N 43:26) (56) References JP-A-7-165511 (JP, A) JP-A-7-69817 (JP, A) JP-A-7-33614 (JP, A) JP-A-6-321709 (JP, A) JP-A-6-312907 (JP, A) JP-A-6-135805 (JP, A) JP-A-5-201810 JP-A-62-270506 (JP, A) JP-A-2-258703 (JP, A) JP-A-3-184904 (JP, A) JP-A-2-279606 (JP, A) JP-A-2-157203 (JP, A) JP-A-63-88103 (JP, A) JP-A-62-292702 (JP, A) JP-A-62-48603 (JP, A) JP-A-61-212503 (JP JP, A) JP-A-61-91108 (JP, A) JP-A-7-48206 (JP, A) JP-A-2-42007 (JP, A) (58) The field (Int.Cl. ^6, DB name) A01N 43/80 A01N 37/34 A01N 43/26

Claims (5)

(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) a general formula: (Wherein R ³ is a hydrogen atom or a hydrocarbon group, and R ⁴ and R ⁵ are a hydrogen atom or a halogen atom, which may be the same as or different from each other). And an isothiazolone compound represented by the general formula (C): (Wherein R ⁶ and R ⁷ are a hydrogen atom, a halogen atom or an alkyl group, and these may be the same as each other;
And a dithiol compound represented by the formula (1): 2. The industrial antibacterial agent according to claim 1, wherein 1 to 200 parts by weight of the component (B) and 1 to 100 parts by weight of the component (C) are blended per 100 parts by weight of the component (A). 3. The component (D) further comprises 3,3,4,4
The industrial antibacterial agent according to claim 1, which comprises -tetrachlorotetrahydrothiophene-1,1-dioxide. 4. The amount of component (D) is 1 per 100 parts by weight of the total amount of component (A), component (B) and component (C).
The industrial antibacterial agent according to claim 3, wherein the amount is from 200 to 200 parts by weight. 5. The industrial antibacterial agent according to claim 1, wherein at least a triol compound is used as the solvent.