JPH0753641B2 - Industrial fungicide - Google Patents

Description

The present invention relates to an α-chlorobenzaldoxime acetate derivative represented by the formula (I) and a 3,3,
The present invention relates to a novel industrial fungicide containing 4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and utilizing the synergistic effect of the both. The industrial bactericide of the present invention, in particular,
It is preferably used in an industrial water system for paper pulp production.

(Prior Art) 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 is generated by the multiplication of bacteria, filamentous fungi and yeasts, and the water channel in which the pulp slurry flows, particularly the rough wall surface where the slurry is in contact, a cheest, a flow box, a 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.

Furthermore, even in a circulating water system for cooling metal working oils, microorganisms multiply and hinder the cooling performance and emulsifying properties of the working oils, and a bad odor is generated, which deteriorates the work environment and is not desirable for public health. It is happening.

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, and quaternary ammonium salts have hitherto been used. Compounds and the like have been used, but these compounds are toxic to the human body, give off a bad odor or 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 research on a bactericide to eliminate the above-mentioned drawbacks. The present invention has the following formula (Wherein n is an integer of 0 to 2) and an α-chlorobenzaldoxime acetate derivative represented by the following formula 3,3,4,4-Tetrachlorotetrahydrothiophene-1,1-
It is an industrial bactericide characterized by containing a dioxide.

The compound represented by the formula (I) is a fungicide described in JP-B-51-33171, and the compound represented by the formula (II) is also a fungicide described in U.S. Pat. No. 2957887. Is.

Each of these bactericides is not satisfactory as an industrial bactericidal agent because the bactericidal effect is insufficient such that the effect is limited to a certain type of microorganism and the effect is lacking in sustainability.

The industrial bactericide of the present invention exerts an extremely excellent bactericidal action which cannot be expected at all by individual constituent components, and is broad against harmful microorganisms such as filamentous fungi, bacteria and yeasts regardless of its type. Has scope.

Examples of the compound of formula (I) in the present invention include α
-Chlorbenzaldoxime acetate, α-chloro-
4-chlorobenzaldoxime acetate, α-chloro-2,4-dichlorobenzaldoxime acetate and the like can be mentioned.

These compounds are not limited to one kind when compounded, and two or more kinds may be used in combination.

The compounding ratio of the compound represented by the formula (I) and the compound (II) represented by the formula (II) is usually 1/10 to 10/1, preferably 1/5 to 5/1 (weight ratio). . At this ratio, a practically satisfactory effect can be achieved.

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 does not matter at all that a stabilizer, a surfactant and the like are added to the industrial bactericidal agent 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 10 parts of α-chlorobenzaldoxime acetate 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-
Dioxide 10 parts Diethylene glycol monomethyl ether 77 parts Solpol 900A (manufactured by Toho Kagaku) 3 parts Example 2 α-chloro-4-chlorobenzaldoxime acetate 10 parts 3,3,4,4-tetrachlorotetrahydrothiophene-1, 1-
Dioxide 10 parts Diethylene glycol monomethyl ether 77 parts Solpol 900A (supra) 3 parts Example 3 α-chlorobenzaldoxime acetate 15 parts 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-
Dioxide 5 parts Diethylene glycol monomethyl ether 77 parts Solpol 900A (supra) 3 parts Example 4 α-chloro-4-chlorobenzaldoxime acetate 15 parts 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-
Dioxide 5 parts Diethylene glycol monomethyl ether 77 parts Solpol 900A (supra) 3 parts Comparative Example 1 α-chlorobenzaldoxime acetate 20 parts Diethylene glycol monomethyl ether 77 parts Solpol 900A (supra) 3 parts Comparative Example 2 α-chloro-4- Chlorbenzaldoxime acetate 20 parts Diethylene glycol monomethyl ether 77 parts Solpol 900A (supra) 3 parts Comparative Example 3 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-
Dioxide 20 parts Diethylene glycol monomethyl ether 77 parts Solpol 900A (supra) 3 parts (Effect test) The industrial fungicides prepared in the above Examples 1 to 4 and Comparative Examples 1 to 3 produced slime by the following test method. The preventive effect and the antiseptic effect were investigated.

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 in water of 20 ppm for 7 days over 2 hours and 3 times.

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. Also, measure the number of paper breaks during papermaking,
The bactericidal effect was confirmed.

From Table 1 above, the industrial germicide of the present invention (Examples 1 to 4)
It can be seen that has an excellent bacterial growth inhibitory action.

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 prepared fungicide 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.

Claims (1)

[Claims] 1. The following formula (Wherein n is an integer of 0 to 2) and an α-chlorobenzaldoxime acetate derivative represented by the following formula An industrial bactericide characterized by containing 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide represented by