JPH05117108A - Industrial bactericide - Google Patents

Abstract

PURPOSE:To provide the title bactericide giving markedly synergistic effect, thus giving adequate bactericidal activity at a lower dose than those in the case of using the active ingredients singly, comprising a combination of alpha- chlorobenzaldoxime and another low toxic antibacterial agent. CONSTITUTION:The objective bactericide comprising a combination of (A) alpha-chlorobenzaldoxime and (B) 4,5-dichloro-1,2-dithiol-3-one at the weight ratio A/B=(50:1)-(1:10) esp. (9:1)-(1 :1). It is preferable that the above active ingredients be normally used in the form of liquid one-pack preparation. The amount of this bactericide to be used, when to be added to the process water system in papermaking process or industrial cooling water system, is 0.05-20ml/l, or so or 0.05-50ml/l or so for inhibiting microorganisms growth or for bactericidal use, respectively. Thereby, the above-mentioned merits can be realized.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial germicide and a germicidal method. More specifically, papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metalworking oil agents, fiber oil agents, paints, antifouling paints,
The present invention relates to an industrial germicide and a germicidal method which are useful as antiseptic agents for paper coating liquids, latexes, sizing agents, etc. and for sterilization and bacteriostatic treatment.

[0002]

2. Description of the Related Art Conventionally, in the papermaking process in the paper and pulp industry and in the cooling water system in various industries, slimes due to bacteria and fungi are generated, and there are obstacles such as deterioration of product quality and production efficiency. Are known. In addition, many industrial products such as heavy oil sludge, metalworking oils, fiber oils, paints, various latexes, and sizing agents are decomposed or contaminated by bacteria or fungi, which spoils the product and reduces its value.

Many fungicides have been used to prevent damage by these microorganisms. Traditionally, organic mercury compounds and chlorinated phenol compounds were used, but these drugs are highly toxic to the human body and seafood,
Its use has been regulated because it causes environmental pollution.Recently, relatively low-toxicity organic nitrogen-sulfur compounds, organic chlorine-based compounds, organic bromine-based compounds and organic sulfur-based compounds have been widely used as industrial fungicides. (Dictionary of antibacterial and antifungal agents, Sho 61. Published by Japan Society of Antibacterial and Antifungal).

One of the active ingredients of the present invention, 4,5-dichloro-1,2-dithiole-3-one, is an industrial sterilizer.
It is known as a bacteriostatic agent. For example, Japanese Patent Laid-Open No. 1-15
Japanese Patent No. 1502 discloses the combined use with an α-chlorobenzaldoxime acetate derivative.

[0005]

However, it is desired to reduce the amount of use as much as possible from the viewpoint of pollution, environmental aspects and sterilization cost reduction. On the other hand, 4,5-dichloro-1,2-dithiol-3-one, which is one of the active ingredients of the present invention, and an α-chlorobenzaldoxime acetate derivative shown in JP-A-1-151502. When used in combination, a sufficient effect cannot be obtained when the amount used is reduced, and when these bactericides are used in an industrial system in which reducing substances such as sulfite ions are present, the bactericidal effect is remarkably reduced. There was a problem.

The α-chloro-benzaldoxime, which is one component of the present invention, is a raw material for synthesizing industrial fungicides such as α-chloro-0-acylbenzaldoximes and α-chloro-chlorobenzaldoximes. Known as (intermediate) (Japanese Patent Publication Nos. 50-15844, 54-3664)
No. 7. 51-33171). Further, the present inventors have found that this compound exhibits an effective bactericidal effect even in a small amount in industrial target systems, particularly in reducing industrial target systems.

The present invention provides the above-mentioned α-chloro-benzaldoxime with 4,5-dichloro-1,2 as a second component.
By adding 2-dithiol-3-one, the bactericidal effect is stronger than the bactericidal effect alone, in other words, a similar effect is exhibited in a fraction of the drug amount when used alone, which is remarkably practical. Based on the discovery of synergistic effects. Further, it was confirmed that the bactericidal effect does not decrease even in an industrial system in which a reducing substance such as sulfite ion exists, and the present invention was completed.

[0008]

Thus, according to the present invention, (a) α-chloro-benzaldoxime and (b) 4,5-dichloro-1,2-dithiol-3-one are effective. An industrial fungicide containing as a component is provided. The α-chloro-benzaldoxime of the active ingredient (a) of the present invention has the following formula (I):

[0009]

[Chemical 1] Is a compound represented by. This invention provides the above active ingredient (a), among many low-toxic organic fungicides,
This is based on the discovery of the fact that an extremely excellent synergistic bactericidal effect is obtained when used in combination with 5-dichloro-1,2-dithiole-3-one. The 4,5-dichloro-1,2-dithiol-3-one used in combination is a known organic fungicide, but no example is known in which it is used in combination with the active ingredient (a) or a compound similar thereto.

The active ingredient (a) and 4,5 in the present invention
In the combination with -dichloro-1,2-dithiol-3-one, the ratio at which a synergistic effect is exhibited is 5
It is suitable to be 0: 1 to 1:10, and 20: 1 to
The ratio is preferably 1: 4, more preferably 9: 1 to 1: 1. It is preferable that each active ingredient of the present invention is usually used in the form of a liquid preparation in the form of a single liquid preparation.

In the case of a one-pack formulation, a usual organic solvent or dispersant is used. When the system to be sterilized is various water systems such as process water in the paper manufacturing process and cooling water for factories, consider the solubility and dispersibility of the active ingredient, and use water or a hydrophilic organic solvent and a liquid agent containing a dispersant. Is preferred. As the hydrophilic organic solvent, amides such as dimethylformamide,
Glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycol ethers such as tripropylene monomethyl ether, alcohols having up to 8 carbon atoms Alternatively, esters such as methyl acetate, ethyl acetate, 3-methoxydibutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, propylene carbonate and the like can be mentioned.

As the dispersant, a cationic surfactant,
Anionic surfactants, nonionic surfactants or amphoteric surfactants are suitable, and nonionic surfactants are preferred from the viewpoint of stability as a preparation. Examples of the nonionic surfactant include higher alcohol ethylene oxide adducts (ethylene oxide is abbreviated as EO hereinafter), alkylphenol (EO) adducts, fatty acid (EO) adducts, and polyhydric alcohol fatty acid esters. (EO) adduct,
Higher alkylamine (EO) adducts, fatty acid amide (EO) adducts, fat and oil (EO) adducts, propylene oxide [P. Abbreviated as O.) (EO) copolymer, alkylamine (PO) (EO) copolymer adduct, glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, Examples thereof include fatty acid ester of sugar, alkyl ether of polyhydric alcohol, and alkylolamide.
The blending ratio of these preparations is such that the total amount of the bactericidal active ingredients (a) and (b) is 1 to 50 parts by weight, and the dispersant is at least 0.01 parts by weight based on 1 part by weight of the total of the active ingredients. And the balance is preferably a hydrophilic organic solvent.

When the system to be sterilized is an oil system such as heavy oil sludge, cutting oil, oil paint, etc., it is preferable to prepare a one-pack formulation using a hydrocarbon solvent such as kerosene, heavy oil or spindle oil. You may use the various surfactants mentioned above. The addition amount of the bactericide of the present invention varies depending on the object to be sterilized, but especially when it is added to the process water system of the paper manufacturing process or the industrial cooling water system, as the concentration (bacteriostatic concentration) for suppressing the growth of microorganisms, , Usually 0.0 as the total concentration of active ingredients
Addition of about 5 to 20 ml / l is sufficient. When used in a bactericidal manner, the total concentration of active ingredients is 0.
The objective can be achieved with 05 to 50 ml / l.

In the present invention, when the two active ingredients (a) and (b) are added at the same time, it is convenient to use the same formulation as described above, but the long-term storage stability of the formulation and the like are important points. When it is preferable to separate each of them in the above, or when they are added separately, they are used as separate formulations. Therefore, according to the present invention, there is further provided an industrial sterilization method characterized by adding the active ingredient (a) and the active ingredient (b) to the industrial sterilization target system.

Also in this case, it is usually convenient to make each preparation a liquid preparation. For example, such a formulation can be prepared by adding the above-mentioned organic solvent or dispersant. Of course, for the sterilization and bacteriostatic target systems in which the active ingredients of the present invention can be directly dissolved or dispersed, the active ingredients can be directly added separately and used. The active ingredients (a) and (b) of the present invention exert an excellent synergistic effect in an industrial sterilization target system based on their synergistic effects. Therefore, even when each of the active ingredients (a) and (b) is used at a concentration at which a bactericidal effect cannot be obtained by itself, it is possible to exhibit the intended bactericidal effect.

[0016]

[Examples] Formulation examples that are examples of the present invention are shown below. All parts in the examples are parts by weight. (Formulation Example 1) α-chloro-benzaldoxime 15 parts 4,5-dichloro-1,2-dithiol-3-one 2 parts Diethylene glycol monomethyl ether 83 parts (Formulation Example 2) α-chloro-benzaldoxime 15 parts 4,5-Dichloro-1,2-dithiol-3-one 10 parts Diethylene glycol monomethyl ether 40 parts Polyethylene glycol 200 35 parts (Formulation Example 3) α-chloro-benzaldoxime 15 parts 4,5-dichloro-1,2 -Dithiol-3-one 4 parts Diethylene glycol monomethyl ether 76 parts Dimethylformamide 5 parts (Comparative formulation example 1) 4,5-Dichloro-1,2-dithiol-3-one 20 parts Diethylene glycol monomethyl ether 80 parts (Comparative formulation example 2) ) Α-Chloro-benzaldoxime 20 parts Diethylene glycol monomethyl ether 80 parts (Test Example 1) [each] Synergistic effect confirmation test based on the blending ratio of components] White water (pH 5.1, SO ₃ ^2- 27ppm, Bacillus, Micrococcus, Pseudomonas, Flavobacterium) collected from a newsprint machine (acidic papermaking) at a paper mill , Mainly Alcaligenes), 5 ppm was added as the total amount of various active ingredients, and the mixture was shaken at 37 ° C. for 30 minutes.
Then, the viable cell count was measured, and the bactericidal rate for the initial bacterial count (7.5 × 10 ⁵ cells / ml) was determined. (Test Results) The test results are shown in Table 1.

[0017]

[Table 1] A: α-chloro-benzaldoxime B: 4,5-dichloro-1,2-dithiol-3-one C: α-chloro-benzaldoxime acetate Note) No. 2 to 8 in Table 1 are the inventions No.
1 and Nos. 9 to 13 are comparative examples. Comparative examples No. 11 to 13
Is a combination described in Japanese Patent Laid-Open No. 1-151502 introduced in the prior art. (Test Example 2) Newspaper papermaking process at a certain paper mill (acid papermaking,
pH 4.5, SO ₃ ^2- 70ppm, Bacillus, Micrococcus, Pseudomonas, Flavobacterium, Alcaligenes spp.)
Immediately after that, the viable cell count was measured. (Test Results) The test results are shown in Table 2.

[0018]

[Table 2]

Claims (2)

[Claims] 1. α-Chloro-benzaldoxime and 4,
An industrial bactericide containing 5-dichloro-1,2-dithiol-3-one as an active ingredient. 2. α-Chloro-benzaldoxime and 4,
A method for industrial sterilization, which comprises adding 5-dichloro-1,2-dithiol-3-one simultaneously or separately for sterilization.