JPH0774128B2 - Industrial fungicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an α-chlorobenzaldoxime acetate derivative represented by the general formula (I) and 4,5-dichloro-1,2-
The present invention relates to a novel industrial bactericidal agent containing dithiol-3-one (hereinafter sometimes abbreviated as "compound (II)") and utilizing the synergistic effect of the two. This industrial fungicide is
It is preferably used in industrial water systems related to paper pulp production.

(Prior art and problems) Conventionally, wastewater from the papermaking process in the pulp and paper industry,
In various water systems such as circulating cooling water in various industrial fields, it is harmful to water-based paints, coating liquids for paper, latex, printing paste, leather, etc. made using industrial water. It is easy for various microorganisms to multiply and proliferate, which causes a decrease in productivity and quality.

In particular, in the water system in the pulp and paper industry, slime has recently been generated due to the multiplication of filamentous fungi and yeasts, and the channel in which the pulp slurry flows, especially the rough wall or chest where the slurry contacts, the flow box, the transport pipe, In addition, slime is deposited and formed in a place where the flow velocity of the pulp slurry becomes low and stagnates. This slime is often detached, causing paper scraps and paper pulp product contamination, as well as causing various disorders due to microbial growth.

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

Further, even in a circulating water system for cooling metalworking oil agents, microorganisms multiply and hinder the cooling performance and emulsifying properties of the oilworking agents, and a bad odor is generated, which worsens the working environment and is a phenomenon unfavorable to public health. Is caused.

Other obstacles due to the propagation of harmful microorganisms are also found in industrial products such as water-based paints, paper coating fluids, polymer latex, paper pulp, glue, leather and metalworking fluids.

By the way, as agents for suppressing or controlling the generation of harmful microorganisms in the water system or the industrial products, for example, organometallic compounds, organochlorine compounds, organosulfur compounds, quaternary ammonium salts have hitherto been used. Although compounds and the like have been used, these compounds are toxic to the human body, emit a foul odor and an offensive odor, and cause undesirable phenomena such as foaming. In addition, these control agent-containing water systems, when they are thrown into general rivers or the sea, have an adverse effect on fish and shellfish, causing environmental problems.

(Object, Structure and Effect of the Invention) The present inventors have completed the present invention as a result of intensive studies to eliminate the above-mentioned drawbacks of industrial germicides.

That is, the present invention is as follows.

The following general formula (In the formula, n represents an integer of 0 to 2) and an α-chlorobenzaldoxime acetate derivative represented by the following formula: An industrial fungicide containing 4,5-dichloro-1,2-dithiol-3-one represented by the formula (1) in a weight ratio of (1:10) to (10: 1).

The compound represented by the general formula (I) is an active ingredient of the fungicide described in JP-B-51-33171, and
The compound (II) is an active ingredient of the fungicide described in JP-B-52-14294.

Each of these bactericides has an insufficient bactericidal effect such as limited effect on a certain type of microorganisms, and lacks in sustainability of the effect, so that it is not yet satisfactory as an industrial bactericidal agent.

The industrial bactericide of the present invention exerts an extremely excellent bactericidal effect which can not be expected at all by the individual constituent components, and is irrespective of the type against harmful microorganisms such as filamentous fungi, bacteria and yeasts. Has a wide range of applications.

Examples of the compound represented by the general formula (I) in the present invention include α-chlorobenzaldoxime acetate, α-chloro-4-chlorobenzaldoxime acetate, α-
Examples thereof include chloro-2,4-dichlorobenzaldoxime acetate. These compounds are 1
It is not limited to only one kind, and two or more kinds may be used in combination.

The compounding ratio (weight) of the compound represented by the general formula (I) and the compound (II) is (1:10) to (10: 1), preferably (1: 5) to (5: 1). Is. If either one is too small, a satisfactory effect cannot be obtained.

The industrial germicide of the present invention is basically prepared by uniformly mixing the above-mentioned two components, but it is generally used as an aqueous solution, a solvent solution, 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. In addition, the industrial bactericide of the present invention may be used by supporting it on any carrier, and the use mode is not particularly limited, and various methods can be adopted.

The amount of this industrial bactericide to be added varies depending on the concentration of microorganisms, but generally 0.01 to 100 ppm in the case of a water-based system in the field of the pulp and paper industry, a water-based paint, a paste,
In the case of leather and the like, it is 1 to 500 ppm, and a good bactericidal effect can be obtained at this level.

It is acceptable to add a stabilizer, a surfactant, etc. to the industrial bactericide of the present invention within a range that does not impair the object of the present invention.

(Examples and Comparative Examples) Industrial fungicides were prepared according to the following formulations. All parts in the examples are parts by weight.

Example 1 α-chlorobenzaldoxime acetate 10 parts Compound (II) 10 parts Diethylene glycol monomethyl ether 77 parts Lapizole B-80 (manufactured by NOF CORPORATION) 3 parts Example 2 α-chloro-4-chlorobenzaldoxime acetate
10 parts Compound (II) 10 parts Diethylene glycol monomethyl ether 77 parts Lapizole B-80 (supra) 3 parts Example 3 α-chlorobenzaldoxime acetate 15 parts Compound (II) 5 parts Diethylene glycol monomethyl ether 77 parts Lapizole B-80 (Nippon Yushi Co., Ltd.) 3 parts Example 4 α-chloro-4-chlorobenzaldoxime acetate
15 parts Compound (II) 5 parts Diethylene glycol monomethyl ether 77 parts Lapizole B-80 (previously mentioned) 3 parts Comparative Example 1 α-chlorobenzaldoxime acetate 20 parts Diethylene glycol monomethyl ether 77 parts Lapizole B-80 (Nippon Oil & Fats Co., Ltd.) 3 parts Comparative Example 2 α-chloro-4-chlorobenzaldoxime acetate
20 parts Diethylene glycol monomethyl ether 77 parts Lapizole B-80 (supra) 3 parts Comparative Example 3 Compound (II) 20 parts Diethylene glycol monomethyl ether 77 parts Lapizole B-80 (supra) 3 parts (Effect test) The above-mentioned Examples 1 to 1 For the industrial bactericides prepared in Example 4 and Comparative Examples 1 to 3, the slime generation preventing effect and the antiseptic effect were examined by the following methods.

Test Example 1 [Test for Prevention of Bacterial Proliferation and Slime Generation in Wastewater After Paper Making Process] In a paper making process of a certain paper mill, the industrial bactericide prepared in the above Examples 1 to 4 and Comparative Examples 1 to 3 was applied to a white water bit. The number of microorganisms in white water was measured by adding the solution to the concentration of 20 ppm for 7 days over 2 hours and 3 times a day.

As a test method, a sample of white water was diluted with sterilized water, a certain amount of this was sampled in a petri dish, and dissolved Waxman agar medium was injected, 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. The number of paper breaks during papermaking was also measured to confirm the sterilization effect.

From the results shown in Table 1 above, it can be seen that the industrial fungicides of the present invention (Examples 1 to 4) have an excellent bacteriostatic effect.

Test Example 2 [Bacterial growth prevention test in a papermaking coating solution] To a starch-based coating solution having a pH of 10.0, a broth liquid medium and a coating solution which has been spoiled in advance were added and stirred, and the concentration was adjusted to 300 ppm as described above. The adjusted germicide was added.

After storing this 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 below.

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Claims (1)

[Claims] 1. The following general formula (In the formula, n represents an integer of 0 to 2) and an α-chlorobenzaldoxime acetate derivative represented by the following formula: An industrial fungicide containing 4,5-dichloro-1,2-dithiol-3-one represented by the formula (1) in a weight ratio of (1:10) to (10: 1).