JPH01151502A - Industrial germicide - Google Patents

Abstract

PURPOSE:To obtain an industrial germicide, capable of exhibiting excellent inhibitory action on microbial propagation by synergistic effects and useful for industrial water systems related to production of paper and pulp, by blending an alpha-chlorobenzaldoxime acetate derivative with other compounds in a specific proportion. CONSTITUTION:An industrial germicide, obtained by homogeneously mixing two ingredients of an alpha-chlorobenzaldoxime acetate derivative expressed by formula I (n is 0-2), e.g., alpha-chlorobenzaldoxime acetate or alpha-chloro-4- chlorobenzaldoxime acetate, with 4,5-dichloro-1,2-dithiol-3-one expressed by formula II at 1:10-10:1 weight ratio and used as an aqueous solution, solution in a solvent, such as alcoholic, ketonic or ethereal solvent, or emulsion, dispersion, etc. The amount of the above-mentioned germicide is 0.01-100ppm in the case of water systems in the field of paper and pulp industry and 1-500ppm in the field of water-color coatings, pastes, leathers, etc., to provide excellent germicidal effects.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to an α-chlorobenzaldoxime acetate derivative represented by the general formula (1) and 4,5-dichloro-1
,2-dithiol-3-one (hereinafter referred to as "compound (■)")
It is sometimes abbreviated as. ) and which utilizes the synergistic effect of both. This industrial fungicide is suitably used in industrial water systems related to the production of Giju pulp.

(Prior art and problems) Conventionally, wastewater from the papermaking process in the pulp and paper industry,
It is harmful to various water systems such as circulating cooling water in various industrial fields, as well as water-based paints, paper coating fluids, latex, printing pastes, leather, etc. that are made using industrial water. microorganisms are likely to multiply, which causes a decline in productivity and quality.

In particular, in water systems in the pulp and paper industry, slime has recently been generated due to the proliferation of filamentous fungi and yeasts, and slime has been generated in waterways where pulp slurry flows, especially in areas with rough walls that come in contact with slurry, chests, flow boxes, transport pipes, etc. In other places where the flow rate of the pulp slurry is low and stagnates, slime is formed. This slime often detaches, causing paper scraps and contamination of Gi pulp products, as well as causing various problems due to the growth of microorganisms.

The occurrence of such failures becomes a particularly serious problem when high-speed machines are used, resulting in a significant decrease in productivity and economic loss.

Furthermore, in the circulating water system for cooling metal processing fluids, microorganisms multiply and multiply, impairing the cooling performance and emulsifying properties of processing fluids, and producing bad odors, deteriorating the working environment, which is an undesirable phenomenon in terms of public health. is causing the

Other problems caused by the growth of harmful microorganisms occur in industrial products such as water-based paints, paper coatings, polymer latex, paper pulp, glues, leather, and metalworking fluids.

By the way, as agents for suppressing or controlling the occurrence of harmful microorganisms in the water system or industrial products, for example, organic metal compounds, organic chlorine compounds, organic sulfur compounds, and quaternary ammonium salts have been used. Compounds have been used, but these compounds are toxic to the human body, emit foul odors and foreign odors, and also cause undesirable phenomena such as foaming. In addition, when these pesticide-containing water systems are sprayed into rivers, oceans, etc., they have an adverse effect on fish and shellfish, causing problems in terms of environmental conservation.

(Objects, structure, and effects of the invention) The present inventors have completed the present invention as a result of extensive research to eliminate the above-mentioned drawbacks of industrial disinfectants.

That is, the present invention is as follows.

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

The compound represented by the general formula (1) is
It is an active ingredient of the fungicide described in Publication No. 71,
Compound (If) is an active ingredient of a fungicide described in Japanese Patent Publication No. 14294/1983.

Each of these disinfectants has insufficient bactericidal effects, such as being limited to certain types of microorganisms, and lacks long-lasting effects, so they are still unsatisfactory as industrial disinfectants.

The industrial fungicide of the present invention exhibits an extremely excellent bactericidal effect that cannot be expected from the individual constituent components, and is effective against harmful microorganisms such as filamentous fungi, bacteria, and yeast, regardless of their types. Has a wide range of application.

Examples of the compound represented by the general formula (1) in the present invention include α-chlorobenzaldoxime acetate, α-chloro-4-chlorobenzaldoxime acetate, α-
Examples include chloro-2,4-dichlorobenzaldoxime acetate.

These compounds are not limited to only one type, and two or more types may be used in combination.

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

The industrial disinfectant of the present invention is basically prepared by uniformly mixing the above-mentioned two components, but for boat fishing it can be used as an aqueous solution, a solvent solution, an emulsified dispersion, etc.

Examples of solvents that can be used here include alcohol solvents, ketone solvents, ether solvents, and hydrocarbon solvents. Further, the industrial disinfectant of the present invention may be used by being supported on any carrier, and there are no particular restrictions on the mode of use, and various methods can be adopted.

The amount added when using this industrial disinfectant varies depending on the microbial concentration, but - for water systems in fields such as boat fishing and the pulp industry, o, oi ~ 1100 pp; for water-based paints, glues, leather, etc. In the field, it is 1 to 500 ppm, and a good bactericidal effect can be obtained at this level.

There is no problem in adding stabilizers, surfactants, etc. to the industrial disinfectant of the present invention as long as they do not impede the purpose of the present invention.

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

Example 1 α-chlorobenzaldoxime acetate) 10 parts Compound (
II) 10 parts diethylene glycol monomethyl ether 77 parts Lausol B
-80 (manufactured by NOF Corporation) 3 parts Example 2 α-chloro-4-chlorobenzaldoxime acetate 10 parts Compound (n
) 10 parts diethylene glycol monomethyl ether 77 parts Lausol B
-80 (supra) 3 parts Example 3 α-chlorobenzaldoxime acetate 15 parts Compound (■
) 5-part diethylene glycerol
Cole monomethyl ether 77 parts Lausol B
-80 (manufactured by NOF Corporation) 3 parts Example 4 α-chloro-4-chlorobenzaldoxime acetate 15 parts Compound (■
) 5 parts diethylene glycol monomethyl ether 77 parts Lausol B
-80 (as above) 3 parts Comparative Example 1 α-Chlorbenzaldoxime acetate 20 parts Diethylene glycol monomethyl ether 77 parts Lausol B
-80 (manufactured by NOF Corporation) 3 parts Comparative Example 2 α-chloro-4-chlorobenzaldoxime acetate 20 parts Diethylene glycol monomethyl ether 77 parts Lausol B
-80 (mentioned above) 3 parts Comparative Example 3 Compound (n) 20 parts Diethylene glycol monomethyl ether 77 parts Lausol B
-80 (mentioned above) 3 parts (Efficacy test) The industrial fungicides prepared in Examples 1 to 4 and Comparative Examples 1 to 3 above were examined for slime generation prevention effect and antiseptic effect by the following method. .

Test Example 1 [Bacterial growth prevention and slime generation prevention test in wastewater after papermaking process] In the papermaking process of a certain papermaking factory, 1 of the industrial fungicides prepared in Examples 1 to 4 and Comparative Examples 1 to 3 above was added to white water bits. The number of microorganisms in the white water was measured by adding it three times a day for 2 hours so that the concentration in the water was 20 ppm for 7 days.

The test method involved diluting a white water sample with sterilized water, taking a quantitative amount of this in a Petri dish, and pouring dissolved Waxman agar medium into it, mixing it, and solidifying it into a flat plate.

After culturing in a thermostatic chamber (32° C.) for 2 days, microbial colonies generated were measured using a colony counter. The number of paper breaks during papermaking was also measured to confirm the bactericidal effect.

Table 1 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 effect of inhibiting bacterial growth.

Test Example 2 [Bacterial growth prevention test in papermaking coating solution] pHlo, o
The bouillon liquid medium and the previously spoiled coating solution were added to the starch-based coating solution, stirred, and the fungicide adjusted above was added to a concentration of 300 ppm.

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.

Claims (1)

[Claims] The following general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
There are α-chlorobenzaldoxime acetate derivatives represented by (I) (in the formula, n represents an integer of 0 to 2) and the following formula ▲ Numerical formula, chemical formula, table, etc. ▼・・・・・・・・・・・・
(II) 4,5-dichloro-1,2-dithiol-
3-one in a weight ratio of (1:10) to (10:1).